Compound characterization data — Zhen et al., 2026

Guang-Jin Zhen, Ling He, Yanfeng Dang, Chun-Jiang Wang. “Programmable regiodivergent access to non-natural α-amino acids via Cu/Pd-catalyzed asymmetric propargylic substitutions.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007722/v1

methyl (R,E)-2-((4-chlorobenzylidene)amino)-2-methyl-5-phenylpent-4-ynoate
Identifier	3a
¹H NMR (400 MHz, Chloroform-d)	δ 8.29 (s, 1H), 7.78 – 7.66 (m, 2H), 7.43 – 7.36 (m, 2H), 7.36 – 7.30 (m, 2H), 7.29 – 7.23 (m, 3H), 3.79 (s, 3H), 3.24 – 2.84 (m, 2H), 1.68 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 158.6, 137.1, 134.6, 131.6, 129.6, 128.9, 128.2, 127.9, 123.4, 85.5, 83.4, 68.4, 52.5, 30.5, 22.7

methyl (R)-2-amino-2-methyl-5-phenylpent-4-ynoate
Identifier	3a'
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 230 nm); tr = 12.45 and 14.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.34 (m, 2H), 7.33 – 7.22 (m, 3H), 3.77 (s, 3H), 2.88 (d, J = 16.5 Hz, 1H), 2.68 (d, J = 16.5 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 131.6, 128.2, 128.0, 123.2, 85.0, 83.5, 57.8, 52.5, 32.0, 25.9

methyl (R)-2-amino-2-methyl-5-(p-tolyl)pent-4-ynoate
Identifier	3b
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 12.07 and 18.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.27 (d, J = 7.9 Hz, 3H), 7.08 (d, J = 8.1 Hz, 1H), 3.76 (s, 3H), 2.87 (d, J = 16.5 Hz, 1H), 2.66 (d, J = 16.4 Hz, 1H), 2.32 (s, 3H), 1.43 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 138.0, 131.5, 128.9, 120.1, 84.2, 83.6, 57.8, 52.4, 32.0, 25.9, 21.4

methyl (R)-2-amino-5-(4-methoxyphenyl)-2-methylpent-4-ynoate
Identifier	3c
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 230 nm); tr = 19.29 and 29.34 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.30 (d, J = 8.5 Hz, 2H), 6.79 (d, J = 8.6 Hz, 2H), 3.78 (s, 3H), 3.75 (s, 3H), 2.85 (d, J = 16.5 Hz, 1H), 2.65 (d, J = 16.5 Hz, 1H), 1.42 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 159.3, 133.0, 115.3, 113.8, 83.3, 83.3, 57.8, 55.2, 52.5, 32.2, 25.9

methyl (R)-2-amino-5-(4-fluorophenyl)-2-methylpent-4-ynoate
Identifier	3d
HPLC	98 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 8.13 and 8.82 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.31 (m, 2H), 7.01 – 6.92 (m, 2H), 3.76 (s, 3H), 3.09 – 2.49 (m, 2H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 162.3 (d, J = 248.9 Hz), 133.5 (d, J = 8.3 Hz), 119.3 (d, J = 3.6 Hz), 115.5 (d, J = 22.2 Hz), 84.7, 82.5, 57.5, 52.6, 32.2, 26.1
¹⁹F NMR (376 MHz, CDCl₃)	δ −111.46

methyl (R)-2-amino-5-(4-chlorophenyl)-2-methylpent-4-ynoate
Identifier	3e
HPLC	98 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 10.74 and 15.72 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.44 – 7.09 (m, 4H), 3.77 (s, 3H), 3.07 – 2.55 (m, 2H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 133.9, 132.9, 128.5, 121.6, 98.0, 86.1, 82.4, 57.7, 52.5, 32.2, 25.9

methyl (R)-2-amino-5-(4-bromophenyl)-2-methylpent-4-ynoate
Identifier	3f
HPLC	98 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 11.70 and 17.25 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.44 – 7.36 (m, 2H), 7.27 – 7.19 (m, 2H), 3.75 (s, 3H), 2.97 – 2.55 (m, 2H), 1.43 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 133.1, 131.4, 122.1, 122.1, 86.3, 82.5, 57.7, 52.5, 32.1, 25.9

methyl (R)-2-amino-2-methyl-5-(4-(trifluoromethyl)phenyl)pent-4-ynoate
Identifier	3g
HPLC	97 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 8.20 and 12.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.53 (d, J = 8.1 Hz, 2H), 7.47 (d, J = 8.1 Hz, 2H), 3.76 (s, 3H), 2.89 (d, J = 16.6 Hz, 1H), 2.70 (d, J = 16.6 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 131.9, 129.8 (q, J = 32.5 Hz), 127.0, 125.2 (q, J = 3.9 Hz), 122.5, 87.9, 82.3, 57.8, 52.6, 32.1, 25.9
¹⁹F NMR (376 MHz, CDCl₃)	δ −62.83

methyl (R)-2-amino-5-(4-cyanophenyl)-2-methylpent-4-ynoate
Identifier	3h
HPLC	98 % ee (Chiralcel OJ, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 270 nm); tr = 17.13 and 23.68 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.56 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H), 3.76 (s, 3H), 2.89 (d, J = 16.6 Hz, 1H), 2.72 (d, J = 16.6 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.3, 132.3, 131.9, 128.1, 118.4, 111.4, 90.1, 82.1, 57.7, 52.6, 32.0, 25.9

methyl (R)-4-(4-amino-5-methoxy-4-methyl-5-oxopent-1-yn-1-yl)benzoate
Identifier	3i
HPLC	99 % ee (Chiralcel AD, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 13.02 and 16.25 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.95 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 3.91 (s, 3H), 3.77 (s, 3H), 2.91 (d, J = 16.6 Hz, 1H), 2.72 (d, J = 16.6 Hz, 1H), 1.45 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 166.5, 131.6, 129.4, 129.3, 129.3, 127.9, 88.4, 82.9, 57.7, 52.5, 52.1, 32.1, 25.9

methyl (R)-2-amino-2-methyl-5-(m-tolyl)pent-4-ynoate
Identifier	3j
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 250 nm); tr = 10.83 and 14.32 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.23 – 7.14 (m, 3H), 7.13 – 7.06 (m, 1H), 3.77 (s, 3H), 2.88 (d, J = 16.5 Hz, 1H), 2.68 (d, J = 16.5 Hz, 1H), 2.31 (s, 3H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.8, 137.9, 132.3, 128.9, 128.7, 128.1, 122.9, 84.6, 83.7, 57.7, 52.5, 32.3, 26.0, 21.1

methyl (R)-2-amino-5-(3-fluorophenyl)-2-methylpent-4-ynoate
Identifier	3k
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 9.46 and 12.01 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.20 – 7.12 (m, 1H), 7.11 – 7.06 (m, 1H), 7.04 – 6.97 (m, 1H), 6.96 – 6.87 (m, 1H), 3.69 (s, 3H), 2.80 (d, J = 16.5 Hz, 1H), 2.61 (d, J = 16.6 Hz, 1H), 1.37 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 162.2 (d, J = 246.2 Hz), 129.7 (d, J = 8.7 Hz), 127.5 (d, J = 3.1 Hz), 124.9 (d, J = 9.5 Hz), 118.4 (d, J = 22.7 Hz), 115.3 (d, J = 21.1 Hz), 86.1, 82.3 (d, J = 3.3 Hz), 57.7, 52.5, 31.9, 25.8
¹⁹F NMR (377 MHz, CDCl₃)	δ −113.16

methyl (R)-2-amino-5-(3-chlorophenyl)-2-methylpent-4-ynoate
Identifier	3l
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 9.38 and 11.40 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.39 – 7.34 (m, 1H), 7.29 – 7.24 (m, 2H), 7.23 – 7.17 (m, 1H), 3.77 (s, 3H), 2.88 (d, J = 16.5 Hz, 1H), 2.69 (d, J = 16.6 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 133.9, 131.5, 129.7, 129.3, 128.2, 124.8, 86.4, 82.1, 57.7, 52.5, 31.9, 25.9

methyl (R)-2-amino-5-(3-fluorophenyl)-2-methylpent-4-ynoate
Identifier	3m
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 10.25 and 11.90 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.53 (t, J = 1.7 Hz, 1H), 7.46 – 7.38 (m, 1H), 7.33 – 7.28 (m, 1H), 7.15 (t, J = 7.9 Hz, 1H), 3.77 (s, 3H), 2.87 (d, J = 16.5 Hz, 1H), 2.68 (d, J = 16.6 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.5, 134.4, 131.2, 130.3, 129.7, 125.2, 122.0, 86.6, 82.1, 57.8, 52.6, 32.0, 25.9
¹⁹F NMR (377 MHz, CDCl₃)	δ −113.16

methyl (R)-2-amino-2-methyl-5-(o-tolyl)pent-4-ynoate
Identifier	3n
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 230 nm); tr = 12.45 and 14.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.35 (d, J = 7.5 Hz, 1H), 7.23 – 7.14 (m, 2H), 7.14 – 7.06 (m, 1H), 3.76 (s, 3H), 2.94 (d, J = 16.5 Hz, 1H), 2.72 (d, J = 16.5 Hz, 1H), 2.39 (s, 3H), 1.45 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 139.9, 131.9, 129.2, 127.9, 125.3, 122.9, 88.8, 82.3, 57.8, 52.4, 32.2, 25.9, 20.7

methyl (R)-2-amino-5-(2-methoxyphenyl)-2-methylpent-4-ynoate
Identifier	3o
HPLC	95 % ee (Chiralcel OJ, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 230 nm); tr = 11.87 and 13.47 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.38 – 7.31 (m, 1H), 7.27 – 7.19 (m, 1H), 6.91 – 6.81 (m, 2H), 3.86 (s, 3H), 3.76 (s, 3H), 2.93 (d, J = 16.5 Hz, 1H), 2.74 (d, J = 16.5 Hz, 1H), 1.46 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 160.2, 133.4, 129.4, 120.3, 112.4, 110.5, 89.3, 79.9, 57.9, 55.7, 52.4, 32.4, 25.9

methyl (R)-2-amino-5-(2-fluorophenyl)-2-methylpent-4-ynoate
Identifier	3p
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 10.80 and 12.07 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.33 (m, 1H), 7.30 – 7.23 (m, 1H), 7.11 – 6.99 (m, 2H), 3.77 (s, 3H), 2.93 (d, J = 16.6 Hz, 1H), 2.73 (d, J = 16.6 Hz, 1H), 1.46 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 162.8 (d, J = 250.7 Hz), 133.4 (d, J = 1.4 Hz), 129.6 (d, J = 7.9 Hz), 123.7 (d, J = 3.7 Hz), 115.3 (d, J = 21.0 Hz), 111.6 (d, J = 15.9 Hz), 90.5 (d, J = 3.2 Hz), 76.8, 57.7, 52.4, 32.2, 25.8
¹⁹F NMR (377 MHz, CDCl₃)	δ −110.64

methyl (R)-2-amino-2-methyl-5-(naphthalen-2-yl)pent-4-ynoate
Identifier	3q
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 7/93, flow rate 1.0 mL/min, λ = 250 nm); tr = 22.29 and 28.48 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.90 (s, 1H), 7.82 – 7.70 (m, 3H), 7.51 – 7.39 (m, 3H), 3.78 (s, 3H), 2.93 (d, J = 16.5 Hz, 1H), 2.74 (d, J = 16.5 Hz, 1H), 1.47 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 132.9, 132.6, 131.4, 128.6, 127.9, 127.7, 127.6, 126.5, 126.5, 120.5, 85.4, 83.9, 57.9, 52.6, 32.2, 25.9

methyl (R)-2-amino-2-methyl-5-(naphthalen-1-yl)pent-4-ynoate
Identifier	3r
HPLC	94 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 15.88 and 17.79 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.27 (d, J = 8.3 Hz, 1H), 7.85 – 7.75 (m, 2H), 7.62 (d, J = 7.1 Hz, 1H), 7.60 – 7.45 (m, 2H), 7.39 (t, J = 7.7 Hz, 1H), 3.79 (s, 3H), 3.05 (d, J = 16.5 Hz, 1H), 2.84 (d, J = 16.5 Hz, 1H), 1.50 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.7, 133.4, 133.1, 130.4, 128.4, 128.3, 126.7, 126.3, 126.1, 125.2, 120.9, 90.1, 81.5, 58.0, 52.6, 32.5, 26.1

methyl (R)-2-amino-2-methyl-5-(thiophen-2-yl)pent-4-ynoate
Identifier	3s
HPLC	>99 % ee (Chiralcel OJ, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 270 nm); tr = 10.00 and 11.30 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.19 (d, J = 5.2 Hz, 1H), 7.13 (d, J = 3.6 Hz, 1H), 6.96 – 6.90 (m, 1H), 3.76 (s, 3H), 2.89 (d, J = 16.6 Hz, 1H), 2.70 (d, J = 16.6 Hz, 1H), 1.43 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 131.6, 126.7, 126.4, 123.2, 89.1, 57.7, 52.5, 32.3, 25.9

methyl (R)-2-amino-2-methyl-5-(pyridin-3-yl)pent-4-ynoate
Identifier	3t
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 4/94, flow rate 0.5 mL/min, λ = 254 nm); tr = 101.22 and 121.58 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.60 (s, 1H), 8.49 (s, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.20 (dd, J = 7.9, 4.8 Hz, 1H), 3.75 (s, 3H), 2.88 (d, J = 16.5 Hz, 1H), 2.69 (d, J = 16.5 Hz, 1H), 1.43 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 152.4, 148.4, 138.6, 122.9, 88.8, 80.2, 57.7, 52.6, 32.1, 25.9

tert-butyl (R)-3-(4-amino-5-methoxy-4-methyl-5-oxopent-1-yn-1-yl)-1H-indole-1-carboxylate
Identifier	3u
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 2/98, flow rate 0.4 mL/min, λ = 254 nm); tr = 72.67 and 97.50 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.12 (d, J = 8.2 Hz, 1H), 7.70 (s, 1H), 7.65 – 7.58 (m, 1H), 7.41 – 7.27 (m, 2H), 3.78 (s, 3H), 2.96 (d, J = 16.5 Hz, 1H), 2.76 (d, J = 16.6 Hz, 1H), 1.66 (s, 9H), 1.48 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 149.1, 134.5, 130.7, 128.6, 125.1, 123.1, 119.9, 115.2, 103.3, 88.5, 84.2, 79.9, 75.1, 57.9, 52.5, 32.3, 28.1, 25.9

methyl (R)-2-amino-2-methylhex-4-ynoate
Identifier	3v
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 230 nm); tr = 12.71 and 14.27 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.22 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 3.76 (s, 3H), 2.90 – 2.63 (m, 2H), 1.76 (t, J = 2.6 Hz, 3H), 1.60 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.4, 158.4, 137.0, 134.6, 129.6, 128.8, 78.6, 74.5, 68.5, 52.4, 29.9, 22.7, 3.5

methyl (R)-2-((4-chlorobenzylidene)amino)-2,6-dimethylhept-6-en-4-ynoate
Identifier	3w
HPLC	99 % ee (Chiralcel OJ-H, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 272 nm); tr = 11.20 and 13.05 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 5.20 – 5.11 (m, 2H), 3.77 (s, 3H), 2.98 (d, J = 16.7 Hz, 1H), 2.89 (d, J = 16.7 Hz, 1H), 1.81 (s, 3H), 1.62 (s, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.2, 158.5, 137.0, 134.5, 129.6, 128.8, 126.8, 121.0, 84.7, 84.5, 68.3, 52.4, 30.3, 23.6, 22.6

methyl (R)-2-amino-5-(cyclohex-1-en-1-yl)-2-methylpent-4-ynoate
Identifier	3x
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 230 nm); tr = 12.45 and 14.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 6.06 – 5.99 (m, 1H), 3.74 (s, 3H), 2.76 (d, J = 16.5 Hz, 1H), 2.55 (d, J = 16.4 Hz, 1H), 2.12 – 2.02 (m, 4H), 1.66 – 1.53 (m, 4H), 1.38 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.7, 134.2, 120.5, 85.4, 81.9, 57.8, 52.4, 32.0, 29.4, 25.8, 25.5, 22.3, 21.5

methyl (R)-2-((4-chlorobenzylidene)amino)-2-methyltetradec-4-ynoate
Identifier	3y
HPLC	99 % ee (Chiralcel IC, i-propanol/hexane = 1/99, flow rate 1.0 mL/min, λ = 254 nm); tr = 8.56 and 9.27 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.69 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H), 3.75 (s, 3H), 2.87 – 2.80 (m, 1H), 2.78 – 2.71 (m, 1H), 2.20 – 2.03 (m, 2H), 1.59 (s, 3H), 1.46 – 1.37 (m, 2H), 1.34 – 1.27 (m, 4H), 1.27 – 1.18 (m, 10H), 0.88 (t, J = 6.8 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.4, 158.3, 136.9, 134.6, 129.6, 128.8, 83.5, 75.4, 68.4, 52.3, 31.9, 29.8, 29.6, 29.5, 29.3, 29.1, 28.9, 28.8, 22.7, 22.6, 18.7, 14.1

methyl (R)-7-(benzyloxy)-2-((4-chlorobenzylidene)amino)-2-methylhept-4-ynoate
Identifier	3z
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 220 nm); tr = 9.25 and 11.91 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.36 – 7.33 (m, 1H), 7.33 – 7.29 (m, 4H), 7.29 – 7.27 (m, 4H), 4.48 (s, 2H), 3.73 (s, 3H), 3.64 (s, 2H), 3.53 (t, J = 6.2 Hz, 2H), 2.65 – 2.57 (m, 1H), 2.57 – 2.47 (m, 1H), 2.35 – 2.22 (m, 2H), 1.84 – 1.72 (m, 2H), 1.40 (s, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 175.4, 138.8, 138.5, 132.7, 129.6, 128.5, 128.3, 127.6, 127.5, 83.0, 75.2, 72.9, 68.8, 61.9, 52.1, 47.7, 29.6, 29.1, 22.4, 15.6

methyl (R)-2-((4-chlorobenzylidene)amino)-2-methylnon-4-ynoate
Identifier	3aa
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 254 nm); tr = 7.35 and 8.07 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.70 (d, J = 8.6 Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 3.76 (s, 3H), 2.88 – 2.80 (m, 1H), 2.78 – 2.70 (m, 1H), 2.26 – 2.02 (m, 2H), 1.60 (s, 3H), 1.44 – 1.29 (m, 4H), 0.85 (t, J = 7.1 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.4, 158.3, 136.9, 134.6, 129.6, 128.8, 83.4, 75.4, 68.5, 52.3, 30.9, 29.8, 22.6, 21.8, 18.3, 13.5

methyl (R)-8-chloro-2-((4-chlorobenzylidene)amino)-2-methyloct-4-ynoate
Identifier	3ab
HPLC	99 % ee (Chiralcel OJ-H, i-propanol/hexane = 3/97, flow rate 1.0 mL/min, λ = 230 nm); tr = 14.96 and 19.13 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.22 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 3.76 (s, 3H), 3.49 (t, J = 6.6 Hz, 2H), 2.90 – 2.80 (m, 1H), 2.78 – 2.70 (m, 1H), 2.22 – 2.13 (m, 2H), 1.87 – 1.77 (m, 2H), 1.63 – 1.55 (m, 2H), 1.59 (s, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.3, 158.4, 137.0, 134.6, 129.6, 128.8, 82.3, 76.3, 68.4, 52.4, 44.5, 31.4, 29.9, 26.0, 22.6, 18.0

methyl (R)-2-((4-chlorobenzylidene)amino)-2,8-dimethylnon-4-ynoate
Identifier	3ac
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 254 nm); tr = 6.46 and 7.17 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.22 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 3.75 (s, 3H), 2.86 – 2.80 (m, 1H), 2.77 – 2.71 (m, 1H), 2.20 – 2.03 (m, 2H), 1.67 – 1.63 (m, 1H), 1.59 (s, 3H), 1.35 – 1.27 (m, 2H), 0.83 (d, J = 6.7 Hz, 6H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.4, 158.3, 136.9, 134.6, 129.6, 128.8, 83.4, 75.3, 68.5, 52.3, 37.8, 29.8, 27.0, 22.6, 22.1, 16.7

(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 4-((R)-4-amino-5-methoxy-4-methyl-5-oxopent-1-yn-1-yl)benzoate
Identifier	3ad
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.95 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 5.42 (d, J = 5.0 Hz, 1H), 4.91 – 4.78 (m, 1H), 3.77 (s, 3H), 2.90 (d, J = 16.5 Hz, 1H), 2.71 (d, J = 16.5 Hz, 1H), 2.45 (d, J = 8.4 Hz, 2H), 2.13 – 0.98 (m, 32H), 0.92 (d, J = 6.4 Hz, 3H), 0.87 (d, J = 6.6 Hz, 6H), 0.69 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 165.4, 139.5, 131.5, 130.0, 129.3, 127.6, 122.8, 88.2, 82.9, 74.8, 57.7, 56.6, 56.1, 52.5, 50.0, 42.3, 39.7, 39.5, 38.2, 37.0, 36.6, 36.2, 35.8, 32.1, 31.9, 31.9, 28.2, 27.9, 27.8, 25.9, 24.3, 23.8, 22.8, 22.5, 21.0, 19.3, 18.7, 11.8

methyl (R)-2-amino-5-(4-((2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)methyl)phenyl)-2-methylpent-4-ynoate
Identifier	3ae
HPLC	>99 % ee (Chiralcel OD-H, i-propanol/hexane = 40/60, flow rate 1.0 mL/min, λ = 230 nm); tr = 21.66 and 24.16 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.63 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 6.93 – 6.84 (m, 2H), 6.70 – 6.63 (m, 1H), 5.10 (s, 2H), 3.76 (s, 6H), 3.70 (s, 2H), 2.88 (d, J = 16.5 Hz, 1H), 2.69 (d, J = 16.5 Hz, 1H), 2.35 (s, 3H), 1.45 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 170.5, 168.2, 156.0, 139.2, 135.9, 135.5, 133.8, 131.8, 131.1, 130.7, 130.5, 129.1, 127.9, 123.2, 114.9, 112.3, 111.8, 101.2, 85.6, 83.1, 66.2, 57.8, 55.6, 52.5, 31.9, 30.3, 25.8, 13.3

4-ethynylbenzyl 2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate compound with methyl (R)-2-amino-2-methyl-5-(4-((2-(11-oxo-6,11-dihydrodibenzo[b,e]oxepin-2-yl)acetoxy)methyl)phenyl)pent-4-ynoate
Identifier	3af
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 40/60, flow rate 1.0 mL/min, λ = 250 nm); tr = 45.11 and 68.88 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.12 (d, J = 2.4 Hz, 1H), 7.96 – 7.84 (m, 1H), 7.60 – 7.53 (m, 1H), 7.52 – 7.45 (m, 1H), 7.41 (dd, J = 8.4, 2.4 Hz, 1H), 7.40 – 7.33 (m, 3H), 7.31 – 7.21 (m, 2H), 7.02 (d, J = 8.4 Hz, 1H), 5.19 (s, 2H), 5.11 (s, 2H), 3.76 (s, 3H), 3.69 (s, 2H), 2.88 (d, J = 16.5 Hz, 1H), 2.68 (d, J = 16.5 Hz, 1H), 1.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 176.6, 171.1, 160.5, 140.4, 136.3, 135.5, 135.5, 132.8, 132.5, 131.8, 129.5, 129.3, 128.0, 127.8, 127.5, 125.2, 123.2, 121.1, 85.6, 83.2, 73.6, 66.3, 57.8, 52.5, 40.2, 32.1, 25.9

((3aS,5aR,8aR,8bS)-2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-3a-yl)methyl 3-((R)-4-amino-5-methoxy-4-methyl-5-oxopent-1-yn-1-yl)benzoate
Identifier	3ag
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 8.02 – 7.95 (m, 1H), 7.57 (d, J = 7.7 Hz, 1H), 7.37 (t, J = 7.8 Hz, 1H), 4.72 – 4.61 (m, 2H), 4.48 – 4.43 (m, 1H), 4.32 (d, J = 11.8 Hz, 1H), 4.26 (d, J = 8.0 Hz, 1H), 4.00 – 3.92 (m, 1H), 3.87 – 3.78 (m, 1H), 3.78 (s, 3H), 2.89 (d, J = 16.6 Hz, 1H), 2.71 (d, J = 16.6 Hz, 1H), 1.55 (s, 3H), 1.49 – 1.43 (m, 6H), 1.36 (d, J = 6.6 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.4, 165.2, 136.0, 132.9, 130.1, 129.1, 128.5, 128.3, 123.6, 109.1, 108.8, 101.6, 86.2, 82.4, 70.7, 70.5, 70.1, 65.5, 61.3, 57.7, 52.5, 31.9, 26.5, 25.9, 25.8, 25.4, 23.9

methyl (R)-2-amino-2-methyl-5-((8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl)pent-4-ynoate
Identifier	3ah
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.23 – 7.10 (m, 3H), 3.75 (s, 3H), 2.90 – 2.81 (m, 3H), 2.65 (d, J = 16.5 Hz, 1H), 2.55 – 2.44 (m, 1H), 2.43 – 2.34 (m, 1H), 2.32 – 2.21 (m, 1H), 2.20 – 1.92 (m, 5H), 1.74 – 1.44 (m, 5H), 1.42 (s, 3H), 0.89 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 139.9, 136.4, 132.1, 128.9, 125.2, 120.5, 84.2, 83.5, 57.8, 52.5, 50.4, 47.8, 44.3, 37.9, 35.8, 32.0, 31.4, 29.0, 26.3, 25.9, 25.5, 21.5, 13.7

methyl (R)-2-amino-5-(4-((S)-3-(tert-butoxy)-2-((tert-butoxycarbonyl)amino)propan-amido) phenyl)-2-methylpent-4-ynoate
Identifier	3ai
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.76 (s, 1H), 7.42 (d, J = 8.7 Hz, 2H), 7.31 (d, J = 8.7 Hz, 2H), 5.54 – 5.49 (m, 1H), 4.27 (s, 1H), 3.87 – 3.79 (m, 1H), 3.74 (s, 3H), 3.42 (t, J = 8.4 Hz, 1H), 2.85 (d, J = 16.5 Hz, 1H), 2.65 (d, J = 16.5 Hz, 1H), 1.44 (s, 9H), 1.41 (s, 3H), 1.19 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 168.9, 155.6, 137.4, 132.4, 129.0, 119.2, 119.1, 118.8, 84.5, 83.2, 80.3, 74.5, 61.8, 60.4, 57.8, 54.6, 52.5, 32.1, 28.3, 27.4, 25.9

methyl (R)-2-amino-5-(2-(((R)-3-(4-isobutylphenyl)-2-oxobutoxy)methyl)phenyl)-2-methyl pent-4-ynoate
Identifier	3aj
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 1H), 7.25 – 7.11 (m, 5H), 7.09 (d, J = 8.1 Hz, 2H), 5.29 – 5.16 (m, 2H), 3.83 – 3.74 (m, 1H), 3.74 (s, 3H), 2.87 (d, J = 16.5 Hz, 1H), 2.67 (d, J = 16.5 Hz, 1H), 2.45 (d, J = 7.2 Hz, 2H), 1.92 – 1.77 (m, 1H), 1.52 (d, J = 7.2 Hz, 3H), 1.44 – 1.39 (m, 3H), 0.91 (s, 3H), 0.89 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.5, 174.3, 140.5, 137.6, 137.6, 132.2, 129.3, 128.1, 127.6, 127.4, 127.4, 127.2, 122.0, 90.3, 80.6, 64.5, 57.7, 52.5, 45.1, 45.1, 44.9, 32.1, 30.2, 25.9, 22.3, 18.4

(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 4-((R)-4-amino-5-methoxy-4-methyl-5-oxopent-1-yn-1-yl)benzoate
Identifier	3ak
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.94 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 4.96 – 4.85 (m, 1H), 3.76 (s, 3H), 2.98 – 2.57 (m, 2H), 2.16 – 2.05 (m, 1H), 2.00 – 1.84 (m, 2H), 1.77 – 1.64 (m, 3H), 1.61 – 1.48 (m, 2H), 1.40 – 1.22 (m, 1H), 1.18 – 1.01 (m, 3H), 0.99 – 0.84 (m, 6H), 0.77 (d, J = 7.0 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 165.5, 156.7, 131.5, 130.0, 129.3, 127.6, 88.2, 82.9, 75.0, 57.6, 52.5, 49.0, 47.2, 40.9, 34.2, 33.9, 31.4, 26.5, 25.6, 24.9, 23.6, 21.9, 20.7, 16.5

methyl (R)-2-amino-2-ethyl-5-phenylpent-4-ynoate
Identifier	3al
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 9.47 and 16.03 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.44 – 7.33 (m, 2H), 7.31 – 7.24 (m, 3H), 3.77 (s, 3H), 2.90 (d, J = 16.5 Hz, 1H), 2.67 (d, J = 16.5 Hz, 1H), 1.93 – 1.80 (m, 1H), 1.77 – 1.65 (m, 1H), 0.91 (t, J = 7.5 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.1, 131.7, 128.2, 127.9, 123.2, 85.0, 83.5, 61.5, 52.4, 32.4, 30.7, 8.5

methyl (R)-2-amino-2-(3-phenylprop-2-yn-1-yl)hexanoate
Identifier	3am
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 9.82 and 17.55 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.33 (m, 2H), 7.31 – 7.24 (m, 3H), 3.76 (s, 3H), 2.90 (d, J = 16.6 Hz, 1H), 2.67 (d, J = 16.6 Hz, 1H), 1.85 – 1.75 (m, 1H), 1.71 – 1.59 (m, 1H), 1.40 – 1.23 (m, 3H), 1.23 – 1.10 (m, 1H), 0.91 (t, J = 6.9 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.2, 131.6, 128.2, 127.9, 123.2, 84.9, 83.5, 61.1, 52.4, 39.3, 30.9, 26.3, 22.8, 13.9

methyl (R)-2-amino-5-methyl-2-(3-phenylprop-2-yn-1-yl)hexanoate
Identifier	3an
HPLC	98 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 9.31 and 18.49 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.34 (m, 2H), 7.32 – 7.27 (m, 3H), 3.77 (s, 3H), 2.90 (d, J = 16.5 Hz, 1H), 2.68 (d, J = 16.5 Hz, 1H), 1.83 – 1.75 (m, 1H), 1.71 – 1.59 (m, 1H), 1.59 – 1.46 (m, 1H), 1.34 – 1.20 (m, 1H), 1.11 – 0.98 (m, 1H), 0.90 (s, 3H), 0.88 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.3, 131.7, 128.2, 127.9, 123.2, 84.9, 83.5, 61.1, 52.4, 37.4, 33.0, 30.9, 28.2, 22.5, 22.4

methyl (R)-2-amino-2-benzyl-5-phenylpent-4-ynoate
Identifier	3ao
HPLC	88 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 12.65 and 30.54 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.44 – 7.35 (m, 2H), 7.34 – 7.21 (m, 6H), 7.18 (d, J = 6.7 Hz, 2H), 3.73 (s, 3H), 3.20 (d, J = 13.1 Hz, 1H), 3.06 – 2.86 (m, 2H), 2.73 (d, J = 16.5 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.4, 135.8, 131.6, 129.8, 128.4, 128.2, 128.0, 127.1, 123.1, 84.7, 83.9, 61.9, 52.2, 45.2, 30.7

methyl (R)-2-amino-2-benzyl-5-phenylpent-4-ynoate
Identifier	3ap
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 250 nm); tr = 10.79 and 22.81 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 2H), 7.31 – 7.25 (m, 5H), 7.22 – 7.12 (m, 3H), 3.75 (s, 3H), 2.92 (d, J = 16.5 Hz, 1H), 2.79 – 2.67 (m, 2H), 2.60 – 2.48 (m, 1H), 2.20 – 2.08 (m, 1H), 2.06 – 1.96 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.8, 141.1, 131.6, 128.3, 128.3, 128.1, 127.9, 125.9, 123.0, 84.6, 83.7, 60.9, 52.4, 41.1, 31.1, 30.6

(S)-3-amino-3-(3-phenylprop-2-yn-1-yl)dihydrofuran-2(3H)-one
Identifier	3aq
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 25/75, flow rate 1.0 mL/min, λ = 254 nm); tr = 24.59 and 30.88 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.45 – 7.37 (m, 2H), 7.34 – 7.27 (m, 3H), 4.47 – 4.31 (m, 2H), 2.80 (s, 2H), 2.65 – 2.54 (m, 1H), 2.32 – 2.20 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 179.0, 131.7, 128.3, 122.7, 83.7, 83.6, 65.2, 57.7, 35.3, 30.1

methyl (R)-2-amino-2-(3-phenylprop-2-yn-1-yl)oct-7-enoate
Identifier	3ar
HPLC	96 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 8.07 and 8.69 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 2H), 7.32 – 7.25 (m, 3H), 5.89 – 5.68 (m, 1H), 5.08 – 4.86 (m, 2H), 3.76 (s, 3H), 2.89 (d, J = 16.5 Hz, 1H), 2.67 (d, J = 16.5 Hz, 1H), 2.11 – 2.01 (m, 2H), 1.87 – 1.75 (m, 1H), 1.72 – 1.60 (m, 1H), 1.48 – 1.34 (m, 3H), 1.28 – 1.14 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.1, 138.5, 131.6, 128.2, 127.9, 123.2, 114.6, 84.9, 83.5, 61.0, 52.3, 39.3, 33.4, 30.9, 28.9, 23.5

methyl (S)-2-amino-2-(2-(methylthio)ethyl)-5-phenylpent-4-ynoate
Identifier	3as
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 250 nm); tr = 9.14 and 22.13 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.34 (m, 2H), 7.32 – 7.27 (m, 3H), 3.78 (s, 3H), 2.89 (d, J = 16.6 Hz, 1H), 2.71 (d, J = 16.6 Hz, 1H), 2.65 – 2.53 (m, 1H), 2.51 – 2.39 (m, 1H), 2.20 – 2.07 (m, 4H), 2.05 – 1.93 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.4, 131.6, 128.2, 128.1, 122.9, 84.2, 83.9, 60.7, 52.6, 38.6, 31.2, 28.9, 15.5

methyl (R)-5-oxo-2-(3-phenylprop-2-yn-1-yl)pyrrolidine-2-carboxylate
Identifier	3at
HPLC	90 % ee (Chiralcel IC, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 230 nm); tr = 20.08 and 32.65 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.28 (m, 5H), 6.22 (s, 1H), 3.81 (s, 3H), 3.02 (d, J = 16.7 Hz, 1H), 2.83 (d, J = 16.7 Hz, 1H), 2.58 – 2.19 (m, 4H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 172.9, 131.7, 128.4, 128.3, 122.5, 84.1, 83.0, 64.9, 53.1, 30.5, 30.2, 29.8

methyl (R)-2-amino-2-(cyclopropylmethyl)-5-phenylpent-4-ynoate
Identifier	3au
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 9.54 and 11.15 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.33 (m, 2H), 7.31 – 7.23 (m, 3H), 3.76 (s, 3H), 2.91 (d, J = 16.5 Hz, 1H), 2.70 (d, J = 16.5 Hz, 1H), 1.79 – 1.69 (m, 1H), 1.66 – 1.56 (m, 1H), 0.75 – 0.61 (m, 1H), 0.55 – 0.34 (m, 2H), 0.19 – 0.10 (m, 1H), 0.10 – 0.00 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.3, 131.6, 128.1, 127.9, 123.2, 84.9, 83.5, 61.6, 52.3, 44.0, 30.7, 6.1, 4.4, 3.6

methyl (R)-2-amino-2-(3-phenylprop-2-yn-1-yl)pent-4-enoate
Identifier	3av
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 9.79 and 11.23 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.34 (m, 2H), 7.32 – 7.25 (m, 3H), 5.81 – 5.66 (m, 1H), 5.23 – 5.13 (m, 2H), 3.77 (s, 3H), 2.90 (d, J = 16.5 Hz, 1H), 2.69 (d, J = 16.5 Hz, 1H), 2.61 (dd, J = 13.5, 6.8 Hz, 1H), 2.40 (dd, J = 13.5, 8.1 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.7, 132.2, 131.6, 128.2, 127.9, 123.1, 119.7, 84.6, 83.7, 60.8, 52.4, 43.5, 30.6

methyl (R)-2-amino-6-(((benzyloxy)carbonyl)amino)-2-(3-phenylprop-2-yn-1-yl)hexanoate
Identifier	3aw
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 30/70, flow rate 1.0 mL/min, λ = 250 nm); tr = 28.51 and 30.48 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.17 (m, 10H), 5.09 (s, 2H), 4.91 – 4.75 (m, 1H), 3.75 (s, 3H), 3.26 – 3.13 (m, 2H), 2.88 (d, J = 16.6 Hz, 1H), 2.67 (d, J = 16.5 Hz, 1H), 1.88 – 1.76 (m, 1H), 1.74 – 1.62 (m, 1H), 1.57 – 1.37 (m, 3H), 1.34 – 1.17 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.9, 156.3, 136.6, 131.6, 128.5, 128.2, 128.1, 128.0, 123.1, 84.6, 83.7, 66.6, 61.0, 52.5, 40.6, 38.8, 31.0, 29.9, 21.3

methyl (R)-2-amino-13-hydroxy-2-(3-phenylprop-2-yn-1-yl)tridecanoate
Identifier	3ax
HPLC	99 % ee (Chiralcel OJ, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 15.41 and 18.06 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 2H), 7.31 – 7.26 (m, 3H), 3.76 (s, 3H), 3.62 (t, J = 6.6 Hz, 2H), 2.89 (d, J = 16.5 Hz, 1H), 2.66 (d, J = 16.5 Hz, 1H), 1.85 – 1.73 (m, 1H), 1.68 – 1.60 (m, 1H), 1.61 – 1.50 (m, 2H), 1.44 – 1.12 (m, 16H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.2, 131.6, 128.1, 127.9, 123.1, 84.9, 83.5, 62.8, 61.1, 52.3, 39.5, 32.7, 30.9, 29.6, 29.5, 29.4, 29.4, 29.3, 29.3, 25.6, 24.1

methyl (S)-2-((4-chlorobenzylidene)amino)-2-(2-(methylthio)ethyl)non-4-ynoate
Identifier	3ay
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 2/98, flow rate 0.1 mL/min, λ = 250 nm); tr = 64.86 and 70.20 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.32 (s, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 3.77 (s, 3H), 2.87 – 2.71 (m, 2H), 2.65 – 2.48 (m, 2H), 2.43 – 2.23 (m, 2H), 2.15 – 2.10 (m, 5H), 1.47 – 1.32 (m, 4H), 0.86 (t, J = 7.1 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.5, 159.2, 137.0, 134.6, 129.6, 128.8, 83.7, 74.7, 70.6, 52.3, 37.1, 30.9, 28.8, 27.4, 21.8, 18.3, 15.5, 13.5

methyl (R)-2-(4-(((benzyloxy)carbonyl)amino)butyl)-2-((4-chlorobenzylidene)amino)non-4-ynoate
Identifier	3az
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 18.41 and 23.50 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.30 (s, 1H), 7.69 (d, J = 8.5 Hz, 2H), 7.41 – 7.26 (m, 8H), 5.20 – 4.99 (m, 2H), 4.90 – 4.71 (m, 1H), 3.74 (s, 3H), 3.25 – 3.16 (m, 2H), 2.85 – 2.68 (m, 2H), 2.23 – 1.91 (m, 4H), 1.62 – 1.48 (m, 2H), 1.44 – 1.27 (m, 6H), 0.84 (t, J = 7.1 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 172.9, 158.9, 156.3, 136.9, 136.6, 134.7, 130.8, 129.5, 129.4, 128.7, 128.5, 128.0, 83.4, 75.1, 70.9, 66.5, 52.2, 40.7, 36.6, 30.9, 30.0, 27.3, 21.7, 21.1, 18.3, 13.5

methyl (R,E)-2-((4-chlorobenzylidene)amino)-2-methyl-3-phenylpenta-3,4-dienoate
Identifier	4a
¹H NMR (400 MHz, Chloroform-d)	δ 8.31 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H), 7.32 – 7.27 (m, 2H), 7.25 – 7.20 (m, 2H), 7.18 – 7.11 (m, 1H), 5.44 – 5.27 (m, 2H), 3.67 (s, 3H), 1.69 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 209.2, 174.4, 159.6, 137.1, 134.7, 133.5, 129.8, 128.8, 128.4, 127.4, 126.9, 108.4, 80.7, 69.9, 52.7, 27.2

methyl (R)-2-amino-2-methyl-3-phenylpenta-3,4-dienoate
Identifier	4a'
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 17.44 and 19.19 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.31 (d, J = 4.3 Hz, 4H), 7.25 – 7.20 (m, 1H), 5.25 – 5.10 (m, 2H), 3.72 (s, 3H), 1.76 (brs, 2H), 1.56 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.6, 176.7, 134.4, 128.4, 127.8, 127.2, 110.6, 79.4, 58.9, 52.6, 26.9

methyl (R)-2-amino-2-methyl-3-(p-tolyl)penta-3,4-dienoate
Identifier	4b
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 16.80 and 22.82 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.18 (d, J = 8.1 Hz, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.27 – 5.04 (m, 2H), 3.71 (s, 3H), 2.32 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.4, 176.8, 137.0, 131.3, 129.1, 127.6, 110.5, 79.2, 58.8, 52.5, 26.9, 21.0

methyl (R)-2-amino-3-(4-methoxyphenyl)-2-methylpenta-3,4-dienoate
Identifier	4c
HPLC	95 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 16.78 and 20.26 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.23 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.4 Hz, 2H), 5.17 – 5.07 (m, 2H), 3.79 (s, 3H), 3.71 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.3, 176.8, 158.8, 129.0, 126.5, 113.8, 110.1, 79.1, 58.9, 55.2, 52.5, 26.9

methyl (R)-2-amino-3-(4-fluorophenyl)-2-methylpenta-3,4-dienoate
Identifier	4d
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 14.40 and 16.19 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.34 – 7.27 (m, 2H), 7.04 – 6.93 (m, 2H), 5.19 – 5.08 (m, 2H), 3.70 (s, 3H), 1.54 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.5, 176.3, 162.0 (d, J = 246.7 Hz), 130.5 (d, J = 3.4 Hz), 129.6 (d, J = 8.0 Hz), 115.3 (d, J = 21.4 Hz), 79.5, 59.0, 52.6, 27.0
¹⁹F NMR (376 MHz, CDCl₃)	δ −115.08

methyl (R)-2-amino-3-(4-chlorophenyl)-2-methylpenta-3,4-dienoate
Identifier	4e
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 17.05 and 21.31 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.32 – 7.21 (m, 4H), 5.28 – 5.07 (m, 2H), 3.70 (s, 3H), 1.54 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.6, 176.5, 133.1, 133.0, 129.1, 128.5, 109.7, 79.8, 58.9, 52.6, 27.2

methyl (R)-2-amino-2-methyl-3-(4-(trifluoromethyl)phenyl)penta-3,4-dienoate
Identifier	4f
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 12.83 and 14.76 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.60 – 7.52 (m, 2H), 7.48 (d, J = 8.3 Hz, 2H), 5.23 (d, J = 2.5 Hz, 2H), 3.71 (s, 3H), 1.57 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.1, 176.4, 138.5, 129.2 (q, J = 32.6 Hz), 128.1, 125.3 (q, J = 3.7 Hz), 121.4 (d, J = 271.9 Hz), 109.9, 80.3, 58.8, 52.7, 27.5
¹⁹F NMR (377 MHz, CDCl₃)	δ −62.60

methyl (R)-4-(4-amino-5-methoxy-4-methyl-5-oxopenta-1,2-dien-3-yl)benzoate
Identifier	4g
HPLC	94 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 14.36 and 16.27 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.96 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.2 Hz, 2H), 5.24 (s, 2H), 3.90 (s, 3H), 3.69 (s, 3H), 1.57 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.3, 166.8, 139.5, 129.7, 128.7, 127.6, 80.3, 52.7, 52.1, 27.5

methyl (R)-2-amino-2-methyl-3-(m-tolyl)penta-3,4-dienoate
Identifier	4h
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 14.74 and 16.10 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.22 – 7.15 (m, 1H), 7.14 – 7.02 (m, 3H), 5.20 – 5.06 (m, 2H), 3.72 (s, 3H), 2.32 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.4, 176.7, 138.0, 134.3, 128.7, 128.3, 128.1, 124.7, 110.6, 79.2, 58.9, 52.5, 26.8, 21.4

methyl (R)-2-amino-3-(3-methoxyphenyl)-2-methylpenta-3,4-dienoate
Identifier	4i
HPLC	95 % ee (Chiralcel OD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 15.01 and 20.68 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.21 (t, J = 7.9 Hz, 1H), 6.91 – 6.84 (m, 2H), 6.82 – 6.75 (m, 1H), 5.21 – 5.10 (m, 2H), 3.78 (s, 3H), 3.72 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.5, 176.7, 159.5, 135.8, 129.4, 120.0, 113.6, 112.8, 110.5, 79.5, 58.8, 55.1, 52.6, 26.9

methyl (R)-2-amino-3-(3-fluorophenyl)-2-methylpenta-3,4-dienoate
Identifier	4j
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 15.77 and 17.47 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.32 – 7.19 (m, 1H), 7.13 – 7.05 (m, 2H), 6.97 – 6.88 (m, 1H), 5.31 – 5.11 (m, 2H), 3.71 (s, 3H), 1.56 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.8, 176.6, 162.7 (d, J = 245.6 Hz), 136.9 (d, J = 7.7 Hz), 129.8 (d, J = 8.4 Hz), 123.3 (d, J = 2.8 Hz), 114.9 (d, J = 22.5 Hz), 114.1 (d, J = 21.3 Hz), 110.0, 80.0, 58.8, 52.7, 27.3
¹⁹F NMR (377 MHz, CDCl₃)	δ −112.89

methyl (R)-2-amino-3-(3-chlorophenyl)-2-methylpenta-3,4-dienoate
Identifier	4k
HPLC	98 % ee (Chiralcel OJ, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 13.43 and 14.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.39 – 7.34 (m, 1H), 7.27 – 7.16 (m, 3H), 5.24 – 5.13 (m, 2H), 3.71 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.6, 176.4, 136.5, 134.2, 129.5, 128.2, 127.3, 125.7, 109.8, 58.9, 52.7, 27.1

methyl (R)-2-amino-2-methyl-3-(o-tolyl)penta-3,4-dienoate
Identifier	4l
HPLC	95 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 1.0 mL/min, λ = 230 nm); tr = 10.66 and 11.43 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.25 – 7.10 (m, 4H), 5.00 – 4.85 (m, 2H), 3.71 (s, 3H), 2.30 (s, 3H), 1.50 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 205.6, 175.8, 137.3, 133.6, 130.4, 128.9, 127.7, 125.5, 107.9, 77.5, 60.3, 52.3, 25.4, 20.0

methyl (R)-2-amino-2-methyl-3-(naphthalen-2-yl)penta-3,4-dienoate
Identifier	4m
HPLC	94 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 16.71 and 23.59 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.96 – 7.69 (m, 4H), 7.59 – 7.39 (m, 3H), 5.33 – 5.13 (m, 2H), 3.72 (s, 3H), 1.62 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.2, 177.3, 133.3, 132.5, 131.9, 128.1, 128.0, 127.5, 126.3, 126.2, 126.1, 126.0, 111.0, 79.8, 58.3, 52.7, 27.3

methyl (R)-2-amino-2-methyl-3-(thiophen-2-yl)penta-3,4-dienoate
Identifier	4n
HPLC	95 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 10.94 and 12.17 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.23 – 7.17 (m, 1H), 7.02 – 6.89 (m, 2H), 5.31 – 5.15 (m, 2H), 3.73 (s, 3H), 1.58 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.3, 176.3, 136.8, 127.3, 125.2, 125.0, 80.4, 59.3, 52.7, 26.7

methyl (R)-2-amino-2-methyl-3-(4-((2-(11-oxo-6,11-dihydrodibenzo[b,e]oxepin-2-yl)acetoxy)methyl)phenyl)penta-3,4-dienoate
Identifier	4o
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 30/70, flow rate 1.0 mL/min, λ = 254 nm); tr = 31.25 and 40.42 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.05 (d, J = 2.4 Hz, 1H), 7.82 (dd, J = 7.7, 1.4 Hz, 1H), 7.53 – 7.44 (m, 1H), 7.44 – 7.37 (m, 1H), 7.34 (dd, J = 8.5, 2.5 Hz, 1H), 7.29 (d, J = 7.4 Hz, 1H), 7.25 – 7.17 (m, 4H), 6.95 (d, J = 8.4 Hz, 1H), 5.13 – 5.10 (m, 2H), 5.10 – 5.07 (m, 2H), 5.06 – 5.02 (m, 2H), 3.64 (s, 3H), 3.61 (s, 2H), 1.48 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.7, 190.8, 176.6, 171.2, 160.5, 140.4, 136.3, 135.5, 134.7, 134.6, 132.8, 132.5, 129.5, 129.3, 128.3, 128.0, 127.8, 127.6, 125.1, 121.1, 110.3, 79.6, 73.6, 66.4, 58.9, 52.6, 40.2, 27.1

methyl (R)-2-amino-3-(4-((2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)methyl)phenyl)-2-methylpenta-3,4-dienoate
Identifier	4p
HPLC	99 % ee (Chiralcel IA, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 250 nm); tr = 28.89 and 33.57 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.71 – 7.58 (m, 2H), 7.50 – 7.42 (m, 2H), 7.33 – 7.26 (m, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.93 (d, J = 2.5 Hz, 1H), 6.88 (d, J = 9.0 Hz, 1H), 6.66 (dd, J = 9.0, 2.5 Hz, 1H), 5.17 (d, J = 1.9 Hz, 2H), 5.11 (s, 2H), 3.76 (s, 3H), 3.73 – 3.68 (m, 5H), 2.36 (s, 3H), 1.55 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.7, 176.6, 170.6, 168.3, 156.0, 139.2, 135.9, 134.7, 134.6, 133.9, 131.2, 130.8, 130.5, 129.1, 128.2, 128.0, 114.9, 112.4, 111.8, 110.3, 101.2, 79.7, 66.4, 58.8, 55.6, 52.6, 30.4, 27.1, 13.4

methyl (R)-2-amino-2-methyl-3-((8S,9R,13R,14R)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl)penta-3,4-dienoate
Identifier	4q
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.22 (d, J = 8.1 Hz, 1H), 7.08 – 7.00 (m, 2H), 5.17 – 5.07 (m, 2H), 3.72 (s, 3H), 2.92 – 2.84 (m, 2H), 2.55 – 2.44 (m, 1H), 2.47 – 2.32 (m, 1H), 2.32 – 2.22 (m, 1H), 2.21 – 1.89 (m, 4H), 1.68 – 1.36 (m, 9H), 0.90 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.4, 176.8, 138.9, 136.5, 131.7, 128.5, 125.4, 125.1, 110.3, 79.2, 58.8, 52.5, 50.5, 47.9, 44.3, 38.0, 35.8, 31.5, 29.4, 26.8, 26.4, 25.6, 21.5, 13.8

((3aS,5aR,8aR,8bS)-2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-3a-yl)methyl 3-((R)-4-amino-5-methoxy-4-methyl-5-oxopenta-1,2-dien-3-yl)benzoate
Identifier	4r
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.07 – 8.02 (m, 1H), 7.99 – 7.91 (m, 1H), 7.59 – 7.52 (m, 1H), 7.38 (t, J = 7.8 Hz, 1H), 5.24 – 5.12 (m, 2H), 4.71 – 4.61 (m, 2H), 4.47 (d, J = 2.6 Hz, 1H), 4.32 (d, J = 11.8 Hz, 1H), 4.26 (dd, J = 7.9, 1.8 Hz, 1H), 3.96 (dd, J = 13.0, 1.9 Hz, 1H), 3.80 (d, J = 13.8 Hz, 1H), 3.72 (s, 3H), 1.57 – 1.52 (m, 6H), 1.45 (s, 3H), 1.37 (s, 3H), 1.35 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.5, 176.2, 165.7, 135.8, 135.2, 132.7, 132.4, 130.1, 129.7, 128.5, 128.4, 110.0, 109.2, 108.8, 101.6, 79.8, 70.8, 70.5, 70.1, 65.3, 61.3, 59.1, 52.6, 26.9, 26.5, 25.8, 25.6, 24.0

(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 4-((R)-4-amino-5-methoxy-4-methyl-5-oxopenta-1,2-dien-3-yl)benzoate
Identifier	4s
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 7.97 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 5.23 (d, J = 2.0 Hz, 2H), 4.91 (td, J = 10.9, 4.4 Hz, 1H), 3.71 (s, 3H), 2.18 – 2.07 (m, 1H), 2.01 – 1.88 (m, 2H), 1.76 – 1.65 (m, 2H), 1.58 (s, 3H), 1.45 – 1.22 (m, 2H), 1.22 – 1.02 (m, 2H), 0.92 (t, J = 6.5 Hz, 6H), 0.78 (d, J = 6.9 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.1, 176.5, 165.8, 139.2, 129.6, 129.5, 127.6, 110.3, 80.2, 74.8, 58.8, 52.7, 49.1, 47.2, 40.9, 34.3, 33.9, 31.4, 27.3, 26.5, 25.6, 24.9, 23.6, 22.0, 20.7, 16.5

methyl (R)-2-amino-2-ethyl-3-phenylpenta-3,4-dienoate
Identifier	4t
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 13.29 and 15.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.41 – 7.03 (m, 5H), 5.22 – 5.03 (m, 2H), 3.70 (s, 3H), 2.12 – 1.98 (m, 1H), 1.92 – 1.80 (m, 1H), 0.91 (t, J = 7.5 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.0, 176.0, 134.7, 128.4, 127.9, 127.3, 110.1, 79.2, 62.4, 52.4, 31.7, 8.2

methyl (R)-2-amino-2-(1-phenylpropa-1,2-dien-1-yl)decanoate
Identifier	4u
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 6.02 and 6.88 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.30 (d, J = 4.3 Hz, 4H), 7.23 (dd, J = 8.8, 4.4 Hz, 1H), 5.25 – 4.98 (m, 2H), 3.70 (s, 3H), 2.04 – 1.92 (m, 1H), 1.85 – 1.73 (m, 1H), 1.48 – 1.06 (m, 12H), 0.87 (t, J = 6.7 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 176.2, 134.7, 128.4, 128.0, 127.2, 110.3, 79.2, 52.4, 38.8, 31.8, 29.8, 29.4, 29.2, 23.8, 22.6, 14.1

methyl (R)-2-amino-5-methyl-2-(1-phenylpropa-1,2-dien-1-yl)hexanoate
Identifier	4v
HPLC	97 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 5.24 and 5.89 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.33 – 7.27 (m, 4H), 7.26 – 7.20 (m, 1H), 5.18 – 5.07 (m, 2H), 3.70 (s, 3H), 2.05 – 1.93 (m, 1H), 1.87 – 1.75 (m, 1H), 1.59 – 1.44 (m, 1H), 1.39 – 1.23 (m, 1H), 1.11 – 0.97 (m, 1H), 0.87 (dd, J = 6.6, 2.3 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.0, 176.2, 134.7, 131.7, 128.5, 128.4, 128.3, 128.0, 127.3, 110.3, 79.2, 62.0, 52.4, 36.6, 32.7, 28.3, 22.6, 22.5

methyl (R)-2-amino-2-benzyl-3-phenylpenta-3,4-dienoate
Identifier	4w
HPLC	87 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 19.38 and 26.87 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.39 – 7.22 (m, 9H), 7.20 – 7.12 (m, 2H), 5.26 – 4.99 (m, 2H), 3.70 (s, 3H), 3.43 (d, J = 13.3 Hz, 1H), 3.09 (d, J = 13.3 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.0, 175.4, 135.9, 134.5, 131.7, 130.2, 128.5, 128.4, 128.3, 128.3, 128.1, 127.4, 127.1, 110.0, 79.6, 62.8, 52.3, 44.5

methyl (R)-2-amino-2-(cyclopropylmethyl)-3-phenylpenta-3,4-dienoate
Identifier	4x
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 16.47 and 21.79 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.35 – 7.27 (m, 4H), 7.26 – 7.18 (m, 1H), 5.19 – 5.03 (m, 2H), 3.72 (s, 3H), 2.10 – 1.69 (m, 2H), 0.77 – 0.63 (m, 1H), 0.56 – 0.38 (m, 2H), 0.21 – 0.11 (m, 1H), 0.10 – 0.03 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 176.4, 134.6, 128.5, 127.9, 127.3, 110.2, 79.3, 52.4, 43.5, 5.9, 4.1, 3.8

methyl (R)-2-allyl-2-amino-3-phenylpenta-3,4-dienoate
Identifier	4y
HPLC	92 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 0.8 mL/min, λ = 250 nm); tr = 12.27 and 15.04 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.36 – 7.28 (m, 4H), 7.26 – 7.19 (m, 1H), 5.84 – 5.64 (m, 1H), 5.26 – 5.04 (m, 4H), 3.71 (s, 3H), 2.78 (ddt, J = 13.7, 7.1, 1.2 Hz, 1H), 2.57 (ddt, J = 13.7, 7.7, 1.1 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 175.6, 134.5, 132.5, 128.5, 128.0, 127.3, 119.9, 109.9, 79.5, 61.6, 52.5, 43.2

methyl (R)-2-amino-2-phenethyl-3-phenylpenta-3,4-dienoate
Identifier	4z
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 250 nm); tr = 29.95 and 33.35 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.35 – 7.23 (m, 7H), 7.21 – 7.12 (m, 3H), 5.23 – 5.04 (m, 2H), 3.71 (s, 3H), 2.84 – 2.72 (m, 1H), 2.60 – 2.48 (m, 1H), 2.37 – 2.25 (m, 1H), 2.20 – 2.07 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 175.8, 141.6, 134.6, 128.5, 128.4, 128.4, 128.1, 127.4, 125.9, 110.1, 79.4, 62.0, 52.5, 40.6, 30.4

methyl (S)-2-amino-2-(tert-butoxymethyl)-3-phenylpenta-3,4-dienoate
Identifier	4aa
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 96/4, flow rate 0.7 mL/min, λ = 250 nm); tr = 11.22 and 14.09 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.49 – 7.07 (m, 5H), 5.16 – 5.05 (m, 2H), 3.86 (d, J = 8.1 Hz, 1H), 3.71 (s, 3H), 3.51 (d, J = 8.1 Hz, 1H), 1.14 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.6, 175.3, 134.4, 128.4, 128.1, 127.3, 107.1, 78.9, 73.2, 67.0, 62.6, 52.4, 27.4

methyl (R)-2-amino-2-(2-(methylthio)ethyl)-3-phenylpenta-3,4-dienoate
Identifier	4ab
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 23.83 and 26.71 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.35 – 7.21 (m, 5H), 5.15 (d, J = 1.7 Hz, 2H), 3.72 (s, 3H), 2.69 – 2.57 (m, 1H), 2.51 – 2.39 (m, 1H), 2.35 – 2.23 (m, 1H), 2.18 – 2.09 (m, 1H), 2.07 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.7, 175.4, 134.3, 128.5, 128.1, 127.5, 109.9, 79.6, 61.8, 52.6, 38.3, 28.8, 15.5

methyl (R)-2-amino-6-(((benzyloxy)carbonyl)amino)-2-(1-phenylpropa-1,2-dien-1-yl)hexanoate
Identifier	4ac
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 250 nm); tr = 10.76 and 12.26 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.41 – 7.17 (m, 10H), 5.21 – 5.03 (m, 4H), 4.98 – 4.61 (m, 1H), 3.69 (s, 3H), 3.31 – 3.06 (m, 2H), 2.09 – 1.94 (m, 1H), 1.88 – 1.80 (m, 1H), 1.73 – 1.57 (m, 1H), 1.53 – 1.39 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.8, 175.7, 156.3, 136.6, 134.4, 128.5, 128.5, 128.1, 128.1, 128.0, 127.4, 110.0, 79.4, 66.6, 61.7, 52.6, 41.1, 35.8, 24.5

methyl (R)-2-amino-2-(3-methoxypropyl)-3-phenylpenta-3,4-dienoate
Identifier	4ad
HPLC	94 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 1.0 mL/min, λ = 250 nm); tr = 17.92 and 24.63 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.32 – 7.27 (m, 4H), 7.26 – 7.20 (m, 1H), 5.21 – 5.03 (m, 2H), 3.70 (s, 3H), 3.37 (t, J = 6.5 Hz, 2H), 3.30 (s, 3H), 2.11 – 1.99 (m, 1H), 1.94 – 1.81 (m, 1H), 1.79 – 1.64 (m, 3H), 1.58 – 1.43 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 175.9, 134.6, 128.4, 128.0, 127.3, 110.2, 79.4, 77.3, 72.6, 61.9, 58.5, 52.5, 35.4, 24.2

methyl (R)-2-amino-2-(1-phenylpropa-1,2-dien-1-yl)oct-7-enoate
Identifier	4ae
HPLC	98 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 1.0 mL/min, λ = 250 nm); tr = 8.85 and 10.74 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.34 – 7.27 (m, 4H), 7.26 – 7.19 (m, 1H), 5.85 – 5.70 (m, 1H), 5.18 – 5.07 (m, 2H), 5.04 – 4.86 (m, 2H), 3.70 (s, 3H), 2.12 – 1.93 (m, 3H), 1.86 – 1.74 (m, 3H), 1.54 – 1.32 (m, 3H), 1.28 – 1.12 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 176.1, 138.7, 134.7, 128.4, 128.0, 127.3, 114.5, 110.2, 79.2, 62.0, 52.5, 38.6, 33.5, 29.0, 23.3

methyl (R)-2-amino-13-hydroxy-2-(1-phenylpropa-1,2-dien-1-yl)tridecanoate
Identifier	4af
HPLC	94 % ee (Chiralcel AS-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 11.45 and 13.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.32 – 7.28 (m, 4H), 7.26 – 7.19 (m, 1H), 5.21 – 5.04 (m, 2H), 3.70 (s, 3H), 3.63 (t, J = 6.7 Hz, 2H), 2.04 – 1.93 (m, 1H), 1.86 – 1.76 (m, 1H), 1.61 – 1.50 (m, 2H), 1.47 – 1.06 (m, 16H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.9, 176.2, 134.7, 128.4, 127.9, 127.3, 110.2, 79.2, 63.0, 62.0, 52.4, 38.8, 32.8, 29.7, 29.5, 29.5, 29.4, 29.4, 25.7, 23.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	5a
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 1.0 mL/min, λ = 230 nm); tr = 15.32 and 23.44 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.80 – 7.71 (m, 2H), 7.45 – 7.27 (m, 9H), 7.09 (s, 1H), 4.85 (s, 2H), 3.77 (s, 3H), 1.98 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 170.5, 159.1, 137.2, 136.6, 136.1, 134.6, 133.5, 129.7, 128.9, 128.9, 128.4, 127.6, 71.9, 61.3, 52.5, 24.3, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-amino-2-methyl-4-phenylbut-3-enoate
Identifier	(R,Z)-5a′
Z:E ratio	>20:1
¹H NMR (400 MHz, Chloroform-d)	δ 7.39 – 7.30 (m, 2H), 7.30 – 7.25 (m, 1H), 7.25 – 7.16 (m, 2H), 7.02 (s, 1H), 4.85 – 4.73 (m, 2H), 3.73 (s, 3H), 2.04 (s, 3H), 1.85 (brs, 2H), 1.59 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.3, 170.5, 137.7, 136.0, 131.8, 128.7, 128.3, 127.5, 60.9, 60.8, 52.5, 25.8, 20.9

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(p-tolyl)but-3-enoate
Identifier	5b
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 26.97 and 36.07 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 1.5 Hz, 4H), 7.04 (s, 1H), 4.84 (s, 2H), 3.76 (s, 3H), 2.35 (s, 3H), 1.98 (s, 3H), 1.71 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.4, 170.5, 159.1, 137.5, 137.2, 135.7, 134.6, 133.6, 133.1, 129.7, 129.0, 128.9, 128.8, 71.9, 61.4, 52.5, 24.3, 21.2, 20.9

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(4-methoxyphenyl)-2-methylbut-3-enoate
Identifier	5c
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AS-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 270 nm); tr = 11.65 and 15.61 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.79 – 7.71 (m, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.23 (d, J = 8.6 Hz, 2H), 7.01 (s, 1H), 6.89 (d, J = 8.7 Hz, 2H), 4.84 (s, 2H), 3.82 (s, 3H), 3.76 (s, 3H), 1.99 (s, 3H), 1.71 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.4, 170.5, 159.1, 159.0, 137.1, 134.8, 134.6, 133.3, 130.2, 129.6, 128.9, 128.4, 113.8, 61.5, 55.2, 52.4, 24.3, 20.9

methyl (R,Z)-3-(acetoxymethyl)-2-((-4-chlorobenzylidene)amino)-4-(4-fluorophenyl)-2-methylbut-3-enoate
Identifier	5d
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 16.28 and 21.18 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.30 – 7.22 (m, 3H), 7.09 – 6.99 (m, 3H), 4.82 (s, 2H), 3.77 (s, 3H), 1.99 (s, 3H), 1.71 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.1, 170.4, 162.1 (d, J = 247.8 Hz), 159.1, 137.3, 136.7, 134.5, 132.3, 132.1 (d, J = 3.5 Hz), 130.6, 130.5, 129.6, 128.9, 115.4, 115.2, 71.8, 61.1, 52.5, 24.2, 20.8
¹⁹F NMR (377 MHz, CDCl₃)	δ −114.05

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(4-chlorophenyl)-2-methylbut-3-enoate
Identifier	5e
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 22.59 and 27.48 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.79 – 7.71 (m, 2H), 7.45 – 7.37 (m, 2H), 7.36 – 7.28 (m, 2H), 7.25 – 7.17 (m, 2H), 7.04 (s, 1H), 4.81 (s, 2H), 3.76 (s, 3H), 1.99 (s, 3H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.0, 170.4, 159.1, 137.4, 137.3, 134.6, 134.5, 133.5, 132.1, 130.1, 129.7, 128.9, 128.5, 71.8, 61.1, 52.5, 24.2, 20.8

methyl (R,Z)-3-(acetoxymethyl)-4-(4-bromophenyl)-2-((4-chlorobenzylidene)amino)-2-methylbut-3-enoate
Identifier	5f
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 23.73 and 28.18 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.79 – 7.71 (m, 2H), 7.52 – 7.44 (m, 2H), 7.44 – 7.37 (m, 2H), 7.19 – 7.12 (m, 2H), 7.02 (s, 1H), 4.81 (s, 2H), 3.76 (s, 3H), 1.98 (s, 3H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 159.1, 137.4, 137.3, 135.0, 134.5, 132.1, 131.4, 130.4, 129.7, 128.9, 121.7, 71.8, 61.1, 52.5, 24.1, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(4-(trifluoromethyl)phenyl)but-3-enoate
Identifier	5g
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 20.53 and 24.94 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.84 – 7.72 (m, 2H), 7.61 (d, J = 8.1 Hz, 2H), 7.45 – 7.36 (m, 4H), 7.14 (s, 1H), 4.82 (s, 2H), 3.77 (s, 3H), 1.98 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.8, 170.3, 159.2, 139.9, 138.8, 137.4, 134.5, 131.8, 129.7, 129.0, 128.9, 127.6, 125.2 (q, J = 3.8 Hz), 124.0 (q, J = 272.3 Hz), 71.7, 60.9, 52.6, 24.1, 20.7
¹⁹F NMR (377 MHz, CDCl₃)	δ −62.59

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(4-cyanophenyl)-2-methylbut-3-enoate
Identifier	5h
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AS-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 23.53 and 29.72 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.65 (d, J = 8.3 Hz, 2H), 7.46 – 7.36 (m, 4H), 7.14 (s, 1H), 4.82 (s, 2H), 3.77 (s, 3H), 1.99 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.6, 170.2, 159.2, 141.0, 139.7, 137.4, 134.3, 132.0, 131.3, 129.6, 129.4, 128.9, 118.6, 111.1, 71.6, 60.8, 52.6, 24.0, 20.7

methyl 4-((R,Z)-2-(acetoxymethyl)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobut-1-en-1-yl)benzoate
Identifier	5i
Z:E ratio	>20:1
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 28.03 and 44.97 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 8.02 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.3 Hz, 2H), 7.13 (s, 1H), 4.83 (s, 2H), 3.92 (s, 3H), 3.77 (s, 3H), 1.98 (s, 3H), 1.71 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 166.7, 159.1, 140.9, 138.5, 137.3, 134.5, 132.3, 129.7, 129.5, 129.0, 128.9, 128.9, 128.8, 71.7, 61.0, 52.5, 52.1, 24.1, 20.7

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(m-tolyl)but-3-enoate
Identifier	5j
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 24.49 and 33.59 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.79 – 7.72 (m, 2H), 7.44 – 7.36 (m, 2H), 7.26 – 7.20 (m, 1H), 7.13 – 7.03 (m, 4H), 4.84 (s, 2H), 3.77 (s, 3H), 2.35 (s, 3H), 1.98 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 170.4, 159.0, 137.8, 137.2, 136.3, 135.9, 134.6, 133.6, 129.6, 129.6, 128.9, 128.3, 128.2, 125.8, 61.3, 52.5, 24.3, 21.4, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(3-methoxyphenyl)-2-methylbut-3-enoate
Identifier	5k
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 22.43 and 30.97 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.80 – 7.72 (m, 2H), 7.44 – 7.35 (m, 2H), 7.27 (d, J = 8.9 Hz, 1H), 7.07 (s, 1H), 6.90 – 6.80 (m, 3H), 4.84 (s, 2H), 3.80 (s, 3H), 3.77 (s, 3H), 1.99 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 170.4, 159.4, 159.1, 137.4, 137.2, 136.7, 134.6, 133.4, 129.6, 129.3, 128.9, 121.2, 114.2, 113.3, 61.3, 55.2, 52.5, 24.2, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(3-fluorophenyl)-2-methylbut-3-enoate
Identifier	5l
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 24.18 and 29.36 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.84 – 7.72 (m, 2H), 7.41 (dd, J = 8.3, 1.3 Hz, 2H), 7.36 – 7.26 (m, 1H), 7.12 – 6.92 (m, 4H), 4.82 (s, 2H), 3.77 (s, 3H), 1.99 (s, 3H), 1.71 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 162.6 (d, J = 245.8 Hz), 159.1, 138.3 (d, J = 7.4 Hz), 137.8, 137.3, 134.5, 132.2, 129.8, 129.7, 129.7, 128.9, 124.6, 124.5, 115.7 (d, J = 21.8 Hz), 114.4 (d, J = 21.1 Hz), 61.1, 52.5, 24.2, 20.8
¹⁹F NMR (377 MHz, CDCl₃)	δ −113.05

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(3-chlorophenyl)-2-methylbut-3-enoate
Identifier	5m
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 0.6 mL/min, λ = 254 nm); tr = 24.31 and 28.65 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.79 – 7.71 (m, 2H), 7.45 – 7.37 (m, 2H), 7.33 – 7.22 (m, 3H), 7.19 – 7.12 (m, 1H), 7.05 (s, 1H), 4.80 (s, 2H), 3.77 (s, 3H), 2.00 (s, 3H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 159.1, 138.1, 138.0, 137.3, 134.5, 134.2, 131.9, 129.7, 129.5, 128.9, 128.9, 127.6, 126.9, 71.7, 61.0, 52.5, 24.1, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(o-tolyl)but-3-enoate
Identifier	5n
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 10.59 and 12.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.27 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.24 – 7.10 (m, 4H), 7.07 (s, 1H), 4.71 (s, 2H), 3.78 (s, 3H), 2.26 (s, 3H), 1.92 (s, 3H), 1.74 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 170.3, 159.0, 137.1, 136.8, 136.2, 135.6, 134.6, 132.8, 129.7, 129.6, 128.9, 128.6, 127.7, 125.6, 71.5, 61.3, 52.4, 24.4, 20.7, 19.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(2-methoxyphenyl)-2-methylbut-3-enoate
Identifier	5o
Z:E ratio	>20:1
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 12.61 and 16.01 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.28 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.31 – 7.26 (m, 1H), 7.26 – 7.18 (m, 1H), 7.08 (s, 1H), 6.93 (t, J = 7.4 Hz, 1H), 6.88 (d, J = 8.3 Hz, 1H), 4.78 (s, 2H), 3.82 (s, 3H), 3.78 (s, 3H), 1.94 (s, 3H), 1.74 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.5, 170.4, 159.2, 157.1, 137.0, 135.9, 134.7, 129.9, 129.7, 129.6, 129.2, 128.8, 125.0, 120.2, 110.5, 71.8, 61.7, 55.5, 52.4, 24.6, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(2-fluorophenyl)-2-methylbut-3-enoate
Identifier	5p
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 14.16 and 17.18 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.32 – 7.26 (m, 2H), 7.16 – 7.02 (m, 3H), 4.80 (s, 2H), 3.77 (s, 3H), 1.94 (s, 3H), 1.73 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.1, 170.3, 160.0 (d, J = 247.2 Hz), 158.8, 138.8, 137.3, 134.6, 130.4 (d, J = 3.0 Hz), 130.4, 129.7, 129.7, 129.5 (d, J = 8.5 Hz), 128.9, 125.9 (d, J = 3.4 Hz), 124.0 (d, J = 14.5 Hz), 123.9 (d, J = 3.7 Hz), 115.5 (d, J = 22.2 Hz), 71.7, 61.4, 52.5, 24.3, 20.7
¹⁹F NMR (377 MHz, CDCl₃)	δ −114.03

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(naphthalen-1-yl)but-3-enoate
Identifier	5q
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 18.83 and 23.16 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.35 (s, 1H), 7.99 – 7.91 (m, 1H), 7.90 – 7.85 (m, 1H), 7.83 – 7.76 (m, 3H), 7.59 – 7.39 (m, 6H), 7.39 – 7.32 (m, 1H), 4.76 (s, 2H), 3.84 (s, 3H), 1.87 (s, 3H), 1.83 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 170.2, 159.0, 138.5, 137.2, 134.6, 133.6, 133.4, 131.7, 131.6, 129.7, 128.9, 128.4, 128.0, 126.3, 126.1, 125.9, 125.3, 124.9, 71.6, 61.5, 52.5, 24.3, 20.6

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(thiophen-2-yl)but-3-enoate
Identifier	5r
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 18.39 and 26.90 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.22 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5 Hz, 2H), 7.38 – 7.33 (m, 1H), 7.17 (s, 1H), 7.12 – 7.07 (m, 1H), 7.07 – 7.01 (m, 1H), 5.02 – 4.90 (m, 2H), 3.75 (s, 3H), 2.03 (s, 3H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.0, 170.7, 159.3, 138.2, 137.2, 134.5, 134.2, 129.7, 129.2, 128.9, 127.2, 127.1, 125.6, 72.2, 61.7, 52.6, 24.1, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(pyridin-3-yl)but-3-enoate
Identifier	5s
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel OJ, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 250 nm); tr = 25.52 and 34.65 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.66 – 8.44 (m, 2H), 8.25 (s, 1H), 7.77 (d, J = 8.5 Hz, 2H), 7.65 – 7.58 (m, 1H), 7.42 (d, J = 8.5 Hz, 2H), 7.34 – 7.26 (m, 1H), 7.09 (s, 1H), 4.82 (s, 3H), 3.77 (s, 3H), 2.00 (s, 3H), 1.73 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 172.7, 170.2, 159.2, 149.8, 148.6, 148.6, 139.2, 137.3, 135.8, 134.4, 130.8, 129.6, 128.9, 123.1, 71.8, 60.8, 52.5, 24.1, 20.7

tert-butyl 3-((R,Z)-2-(acetoxymethyl)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobut-1-en-1-yl)-1H-indole-1-carboxylate
Identifier	5t
Z:E ratio	>20:1
HPLC	99 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 1.0 mL/min, λ = 270 nm); tr = 32.32 and 37.48 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.26 (s, 1H), 8.22 – 8.14 (m, 1H), 7.78 (d, J = 8.5 Hz, 2H), 7.64 (s, 1H), 7.61 – 7.50 (m, 1H), 7.45 – 7.41 (m, 2H), 7.39 – 7.33 (m, 1H), 7.31 – 7.26 (m, 1H), 7.16 (s, 1H), 4.96 – 4.85 (m, 2H), 3.78 (s, 3H), 2.04 (s, 3H), 1.77 (s, 3H), 1.67 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 170.5, 159.2, 149.4, 137.2, 136.8, 135.1, 134.6, 130.1, 129.7, 129.7, 128.9, 124.8, 124.2, 123.3, 122.8, 118.9, 115.7, 115.3, 84.0, 72.3, 62.0, 52.5, 28.1, 24.3, 20.8

methyl (R,Z)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenyl-3-((propionyloxy)methyl)but-3-enoate
Identifier	5u
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 11.31 and 15.35 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.44 – 7.31 (m, 4H), 7.31 – 7.25 (m, 3H), 7.08 (s, 1H), 4.85 (s, 2H), 3.76 (s, 3H), 2.26 (q, J = 7.6 Hz, 2H), 1.72 (s, 3H), 1.09 (t, J = 7.6 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.8, 173.2, 159.0, 137.1, 136.6, 136.1, 134.6, 133.4, 129.6, 128.8, 128.8, 128.3, 127.5, 61.2, 52.5, 27.4, 24.3, 8.9

methyl (R,Z)-2-((4-chlorobenzylidene)amino)-3-((isobutyryloxy)methyl)-2-methyl-4-phenylbut-3-enoate
Identifier	5v
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 10.51 and 13.73 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.76 (d, J = 8.4 Hz, 2H), 7.45 – 7.38 (m, 2H), 7.37 – 7.31 (m, 2H), 7.31 – 7.27 (m, 3H), 7.09 (s, 1H), 4.81 (s, 2H), 3.77 (s, 3H), 2.54 – 2.43 (m, 1H), 1.73 (s, 3H), 1.13 (d, J = 7.0 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.5, 173.1, 159.0, 137.1, 136.6, 136.1, 134.5, 133.7, 129.6, 128.8, 128.7, 128.2, 127.5, 72.0, 61.3, 52.5, 33.9, 24.5, 18.8, 18.8

methyl (R,Z)-2-((4-chlorobenzylidene)amino)-2-methyl-3-(((3-methylbutanoyl)oxy)methyl)-4-phenylbut-3-enoate
Identifier	5w
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 9.61 and 14.99 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.80 – 7.72 (m, 2H), 7.44 – 7.37 (m, 2H), 7.37 – 7.31 (m, 2H), 7.31 – 7.26 (m, 3H), 7.09 (s, 1H), 4.82 (s, 2H), 3.77 (s, 3H), 2.16 – 1.99 (m, 3H), 1.72 (s, 3H), 0.93 (d, J = 6.4 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.1, 172.5, 159.1, 137.2, 136.5, 136.1, 134.6, 133.6, 129.7, 128.8, 128.8, 128.3, 127.6, 71.9, 61.1, 52.5, 43.2, 25.5, 24.4, 22.3

(R)-2-((Z)-benzylidene)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobutyl cyclohexanecarboxylate
Identifier	5x
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 12.76 and 16.17 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.37 – 7.27 (m, 5H), 7.08 (s, 1H), 4.84 – 4.72 (m, 2H), 3.77 (s, 3H), 2.28 – 2.16 (m, 1H), 1.90 – 1.78 (m, 2H), 1.76 – 1.56 (m, 7H), 1.48 – 1.31 (m, 2H), 1.30 – 1.11 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.5, 173.1, 159.1, 137.1, 136.5, 136.1, 134.6, 133.8, 129.7, 128.8, 128.8, 128.3, 127.6, 72.1, 61.2, 52.5, 43.1, 28.8, 28.8, 25.6, 25.3, 24.5

methyl (R,Z)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenyl-3-((pivaloyloxy)methyl)but-3-enoate
Identifier	5y
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.65 mL/min, λ = 270 nm); tr = 16.00 and 21.84 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.37 – 7.23 (m, 5H), 7.09 (s, 1H), 4.82 – 4.70 (m, 2H), 3.77 (s, 3H), 1.73 (s, 3H), 1.16 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 178.0, 173.0, 158.9, 137.1, 136.6, 136.1, 134.5, 134.2, 129.7, 128.8, 128.7, 128.2, 127.6, 72.3, 61.6, 52.5, 38.6, 27.0, 24.7

methyl (R,Z)-3-((acetoxy-d3)methyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	5z
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 13.79 and 17.30 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.79 – 7.72 (m, 2H), 7.44 – 7.25 (m, 7H), 7.09 (s, 1H), 4.85 (s, 2H), 3.77 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 170.5, 159.1, 137.2, 136.5, 136.1, 134.6, 133.4, 129.6, 128.9, 128.8, 128.3, 127.6, 71.8, 61.2, 52.4, 24.2, 20.1 (sept, J = 19.6 Hz)

methyl (R,Z)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenyl-3-(((3-phenylpropanoyl)oxy)methyl)but-3-enoate
Identifier	5aa
Z:E ratio	>20:1
HPLC	99 % ee (Chiralcel AS-H, i-propanol/hexane = 2/98, flow rate 0.6 mL/min, λ = 250 nm); tr = 30.24 and 38.28 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.79 – 7.71 (m, 2H), 7.44 – 7.37 (m, 2H), 7.36 – 7.25 (m, 7H), 7.24 – 7.13 (m, 3H), 7.08 (s, 1H), 4.85 (s, 2H), 3.74 (s, 3H), 2.92 – 2.84 (m, 2H), 2.59 – 2.50 (m, 2H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 172.3, 159.1, 140.3, 137.2, 136.5, 136.1, 134.6, 133.6, 129.7, 128.9, 128.8, 128.5, 128.3, 128.2, 127.6, 126.3, 71.9, 61.4, 52.5, 35.7, 30.7, 24.4

methyl (R,Z)-3-((but-3-enoyloxy)methyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	5ab
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 12.19 and 18.60 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.79 – 7.72 (m, 2H), 7.45 – 7.25 (m, 7H), 7.09 (s, 1H), 5.85 – 5.71 (m, 1H), 5.10 – 4.95 (m, 2H), 4.84 (s, 2H), 3.76 (s, 3H), 2.39 – 2.26 (m, 4H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 172.4, 159.1, 137.2, 136.5, 136.0, 134.5, 133.6, 129.6, 128.9, 128.8, 128.3, 127.6, 115.5, 71.9, 61.3, 52.5, 33.3, 28.6, 24.3

(R)-2-((Z)-benzylidene)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobutyl cyclopent-3-ene-1-carboxylate
Identifier	5ac
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 13.15 and 21.79 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.38 – 7.32 (m, 2H), 7.29 (d, J = 6.9 Hz, 3H), 7.09 (s, 1H), 5.63 (s, 2H), 4.85 (s, 2H), 3.77 (s, 3H), 3.11 – 2.98 (m, 1H), 2.69 – 2.52 (m, 4H), 1.73 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.6, 173.2, 159.1, 137.2, 136.6, 136.1, 134.6, 133.7, 129.7, 128.9, 128.8, 128.3, 127.6, 61.6, 52.5, 41.5, 36.2, 24.5

methyl (R,Z)-3-(((3-(1H-indol-3-yl)propanoyl)oxy)methyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	5ad
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 254 nm); tr = 15.58 and 18.46 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.99 (s, 1H), 7.73 (d, J = 8.5 Hz, 2H), 7.58 – 7.51 (m, 1H), 7.37 (d, J = 8.4 Hz, 2H), 7.34 – 7.23 (m, 6H), 7.21 – 7.15 (m, 1H), 7.13 – 7.04 (m, 2H), 6.94 (d, J = 2.3 Hz, 1H), 4.86 (s, 2H), 3.72 (s, 3H), 3.08 – 2.99 (m, 2H), 2.69 – 2.61 (m, 2H), 1.69 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.2, 172.8, 159.1, 137.2, 136.5, 136.2, 136.0, 134.6, 133.6, 129.6, 128.9, 128.8, 128.3, 127.6, 127.1, 122.0, 121.4, 119.3, 118.6, 114.7, 111.1, 71.9, 61.3, 52.5, 34.7, 24.3, 20.4

methyl (R,Z)-3-(acetoxymethyl)-4-(4-((R)-3-(tert-butoxy)-2-((tert-butoxycarbonyl)amino)propanamido)phenyl)-2-((4-chlorobenzylidene)amino)-2-methylbut-3-enoate
Identifier	5ae
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.75 (s, 1H), 8.23 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.6 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.29 – 7.22 (m, 2H), 7.02 (s, 1H), 5.52 (s, 1H), 4.83 (s, 2H), 4.31 – 4.27 (m, 1H), 3.91 – 3.83 (m, 1H), 3.75 (s, 3H), 3.49 – 3.40 (m, 1H), 1.99 (s, 3H), 1.70 (s, 3H), 1.47 (s, 9H), 1.24 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 170.5, 168.9, 159.1, 155.6, 137.2, 137.2, 136.1, 134.6, 132.9, 132.0, 129.7, 128.9, 119.3, 80.3, 74.6, 71.9, 61.9, 61.3, 54.5, 52.5, 28.3, 27.5, 24.3, 20.9

acetyl((R)-3-((4-chlorobenzylidene)amino)-2-((Z)-4-((((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)carbonyl)benzylidene)-4-methoxy-3-methyl-4-oxobutyl)oxonium
Identifier	5af
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 8.05 – 7.96 (m, 2H), 7.80 – 7.72 (m, 2H), 7.46 – 7.38 (m, 2H), 7.38 – 7.31 (m, 2H), 7.14 (s, 1H), 4.99 – 4.88 (m, 1H), 4.82 (s, 2H), 3.77 (s, 3H), 2.20 – 2.05 (m, 1H), 1.99 (s, 4H), 1.83 – 1.64 (m, 6H), 1.62 – 1.49 (m, 2H), 1.23 – 1.03 (m, 2H), 0.92 (dd, J = 6.8, 3.4 Hz, 6H), 0.79 (d, J = 7.0 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 165.7, 159.1, 140.7, 138.4, 137.3, 134.5, 132.4, 129.8, 129.7, 129.7, 129.5, 128.9, 128.7, 74.9, 71.7, 61.1, 52.5, 47.2, 40.9, 34.3, 31.4, 26.5, 24.2, 23.6, 22.0, 20.8, 20.7, 16.5

(3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 4-((R,Z)-2-(acetoxymethyl)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobut-1-en-1-yl)benzoate
Identifier	5ag
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 8.05 – 7.99 (m, 2H), 7.80 – 7.72 (m, 2H), 7.45 – 7.35 (m, 2H), 7.37 – 7.27 (m, 2H), 7.13 (s, 1H), 5.45 – 5.38 (m, 1H), 4.94 – 4.76 (m, 3H), 3.77 (s, 3H), 2.47 (d, J = 7.3 Hz, 2H), 2.10 – 1.77 (m, 10H), 1.63 – 0.99 (m, 24H), 0.92 (d, J = 6.5 Hz, 3H), 0.87 (dd, J = 6.6, 1.8 Hz, 6H), 0.69 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.3, 165.6, 159.1, 140.7, 139.6, 138.4, 137.3, 134.5, 132.4, 129.8, 129.7, 129.7, 129.5, 129.5, 128.9, 128.7, 128.7, 128.6, 122.8, 74.6, 71.8, 61.0, 56.6, 56.1, 52.5, 50.0, 46.1, 42.3, 39.7, 39.5, 38.2, 37.0, 36.6, 36.1, 35.7, 31.9, 31.8, 28.2, 27.9, 27.8, 24.3, 24.1, 23.8, 22.8, 22.5, 21.0, 20.7, 19.3, 18.7, 11.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-4-(2-((((R)-2-(4-isobutylphenyl)propanoyl)oxy)methyl)phenyl)-2-methylbut-3-enoate
Identifier	5ah
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 7.34 – 7.19 (m, 3H), 7.19 – 7.12 (m, 3H), 7.11 – 7.02 (m, 3H), 5.13 – 5.00 (m, 2H), 4.64 (d, J = 2.0 Hz, 2H), 3.75 (s, 4H), 2.42 (d, J = 7.1 Hz, 2H), 1.88 (s, 3H), 1.87 – 1.75 (m, 1H), 1.68 – 1.59 (m, 4H), 1.47 (d, J = 7.1 Hz, 3H), 0.88 (d, J = 6.7 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.3, 173.1, 170.2, 159.2, 140.6, 138.5, 137.5, 137.2, 135.7, 134.6, 133.9, 131.0, 131.0, 129.7, 129.3, 128.9, 128.4, 128.0, 127.7, 127.1, 71.2, 64.3, 61.1, 52.4, 45.1, 44.9, 30.1, 24.1, 22.3, 20.6, 18.4

((3aS,5aR,8aR,8bS)-2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-3a-yl)methyl 3-((R,Z)-2-(acetoxymethyl)-3-((4-chlorobenzylidene)amino)-4-methoxy-3-methyl-4-oxobut-1-en-1-yl)benzoate
Identifier	5ai
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 8.05 – 7.95 (m, 2H), 7.80 – 7.71 (m, 2H), 7.52 – 7.37 (m, 4H), 7.13 (s, 1H), 4.77 (s, 2H), 4.75 – 4.64 (m, 1H), 4.67 – 4.60 (m, 1H), 4.45 (d, J = 2.6 Hz, 1H), 4.32 (d, J = 11.8 Hz, 1H), 4.32 – 4.22 (m, 1H), 3.99 – 3.90 (m, 1H), 3.84 – 3.75 (m, 4H), 2.01 (s, 3H), 1.72 (s, 3H), 1.53 (s, 3H), 1.45 (s, 3H), 1.34 (d, J = 2.1 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.4, 165.6, 159.1, 137.9, 137.3, 136.5, 134.5, 133.2, 132.4, 130.3, 130.0, 129.7, 129.7, 128.9, 128.7, 128.4, 109.1, 108.8, 101.6, 71.8, 70.7, 70.6, 70.0, 65.4, 61.3, 61.0, 52.5, 26.4, 25.8, 25.4, 24.1, 23.9, 20.7

methyl (R,Z)-3-(acetoxymethyl)-4-(4-((2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)methyl)phenyl)-2-((4-chlorobenzylidene)amino)-2-methylbut-3-enoate
Identifier	5aj
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 40/60, flow rate 1.0 mL/min, λ = 254 nm); tr = 36.46 and 47.99 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.64 (d, J = 8.5 Hz, 2H), 7.49 – 7.39 (m, 2H), 7.39 (s, 2H), 7.32 – 7.25 (m, 3H), 7.08 (s, 1H), 6.94 (d, J = 2.5 Hz, 1H), 6.88 (d, J = 9.0 Hz, 1H), 6.67 (dd, J = 9.0, 2.5 Hz, 1H), 5.14 (s, 2H), 4.83 (s, 2H), 3.77 (d, J = 2.0 Hz, 6H), 3.72 (s, 2H), 2.37 (s, 3H), 1.99 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.1, 170.5, 170.3, 168.2, 159.0, 155.9, 139.2, 137.2, 137.1, 136.1, 135.9, 135.0, 134.5, 133.8, 132.8, 131.1, 130.7, 130.5, 129.6, 129.0, 128.9, 128.9, 128.1, 114.9, 112.4, 111.7, 101.1, 71.8, 66.3, 61.2, 55.6, 52.5, 30.3, 24.2, 20.8, 13.3

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-(4-((2-(11-oxo-6,11-dihydrodibenzo[b,e]oxepin-2-yl)acetoxy)methyl)phenyl)but-3-enoate
Identifier	5ak
Z:E ratio	>20:1
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 30/70, flow rate 1.0 mL/min, λ = 270 nm); tr = 25.01 and 29.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.24 (s, 1H), 8.13 (d, J = 2.4 Hz, 1H), 7.89 (dd, J = 7.7, 1.4 Hz, 1H), 7.80 – 7.72 (m, 2H), 7.60 – 7.51 (m, 1H), 7.49 – 7.46 (m, 1H), 7.45 – 7.27 (m, 8H), 7.08 (s, 1H), 7.03 (d, J = 8.5 Hz, 1H), 5.18 (s, 2H), 5.14 (s, 2H), 4.83 (s, 2H), 3.76 (s, 3H), 3.70 (s, 2H), 1.98 (s, 3H), 1.72 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 173.1, 171.1, 170.4, 160.4, 159.1, 140.4, 137.2, 137.0, 136.3, 136.1, 135.5, 135.0, 134.5, 132.9, 132.7, 132.4, 129.6, 129.4, 129.2, 129.0, 128.9, 128.2, 127.8, 127.5, 125.1, 121.0, 73.5, 71.8, 66.3, 61.2, 52.5, 40.1, 24.2, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-((8S,9R,13R,14R)-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl)but-3-enoate
Identifier	5al
Z:E ratio	>20:1
Diastereomeric ratio	>20:1 dr
¹H NMR (400 MHz, Chloroform-d)	δ 8.23 (s, 1H), 7.78 – 7.71 (m, 2H), 7.43 – 7.36 (m, 2H), 7.27 (d, J = 8.5 Hz, 1H), 7.11 – 7.04 (m, 1H), 7.04 – 6.98 (m, 2H), 4.93 – 4.75 (m, 2H), 3.76 (s, 3H), 3.07 – 2.76 (m, 2H), 2.57 – 2.38 (m, 2H), 2.36 – 2.24 (m, 1H), 2.22 – 1.93 (m, 6H), 1.71 (s, 3H), 1.71 – 1.38 (m, 7H), 0.92 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 170.5, 159.0, 139.3, 137.2, 136.4, 135.9, 134.6, 133.5, 133.4, 129.6, 129.5, 128.9, 126.2, 125.3, 71.9, 61.4, 52.4, 50.4, 47.9, 44.3, 38.1, 35.8, 31.5, 29.3, 26.4, 25.6, 24.3, 21.5, 20.9, 13.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-ethyl-4-phenylbut-3-enoate
Identifier	5am
Z:E ratio	>20:1
HPLC	93 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 260 nm); tr = 8.90 and 11.78 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.21 (s, 1H), 7.81 – 7.73 (m, 2H), 7.46 – 7.33 (m, 4H), 7.31 – 7.27 (m, 3H), 7.19 (s, 1H), 4.78 (s, 2H), 3.75 (s, 3H), 2.27 – 2.04 (m, 2H), 2.00 (s, 3H), 0.94 (t, J = 7.4 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.5, 159.1, 137.2, 136.3, 134.8, 134.7, 134.7, 129.6, 128.9, 128.8, 128.3, 127.5, 75.1, 61.4, 52.2, 30.7, 20.8, 8.1

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)pentanoate
Identifier	5an
Z:E ratio	>20:1
HPLC	92 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 7.37 and 10.29 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.77 (d, J = 8.5 Hz, 2H), 7.44 – 7.28 (m, 7H), 4.77 (s, 2H), 3.75 (s, 3H), 2.17 – 2.01 (m, 2H), 2.00 (s, 3H), 1.41 – 1.27 (m, 4H), 0.88 (t, J = 6.9 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.5, 158.9, 137.1, 136.3, 134.9, 134.7, 134.6, 129.6, 128.9, 128.8, 128.6, 128.5, 128.3, 127.5, 77.3, 77.0, 76.7, 74.9, 61.4, 52.2, 37.6, 25.7, 23.1, 20.8, 13.9

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)decanoate
Identifier	5ao
Z:E ratio	>20:1
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 62.50 and 65.22 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.80 – 7.72 (m, 2H), 7.45 – 7.32 (m, 4H), 7.32 – 7.24 (m, 3H), 7.20 (s, 1H), 4.84 – 4.70 (m, 2H), 3.75 (s, 3H), 2.17 – 2.03 (m, 2H), 2.00 (s, 3H), 1.44 – 1.15 (m, 12H), 0.90 – 0.81 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.0, 170.5, 158.9, 137.1, 136.3, 135.0, 134.7, 134.6, 129.6, 128.9, 128.8, 128.3, 127.5, 74.9, 61.4, 52.2, 37.9, 31.8, 30.0, 29.4, 29.2, 23.5, 22.6, 20.8, 14.0

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)-5-methylhexanoate
Identifier	5ap
Z:E ratio	>20:1
HPLC	92 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 7.05 and 9.81 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.21 (s, 1H), 7.81 – 7.73 (m, 2H), 7.45 – 7.33 (m, 4H), 7.32 – 7.24 (m, 3H), 7.21 (s, 1H), 4.84 – 4.72 (m, 2H), 3.75 (s, 3H), 2.19 – 2.01 (m, 2H), 2.00 (s, 3H), 1.59 – 1.45 (m, 1H), 1.34 – 1.17 (m, 2H), 0.88 (dd, J = 6.6, 2.2 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.4, 158.9, 137.1, 136.3, 134.9, 134.7, 134.6, 129.6, 128.9, 128.8, 128.3, 127.5, 74.8, 61.4, 35.7, 32.3, 28.4, 22.5, 22.5, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((chlorobenzylidene)amino)-2-(cyclopropylmethyl)-4-phenylbut-3-enoate
Identifier	5aq
Z:E ratio	>20:1
HPLC	91 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 9.89 and 22.63 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.25 (s, 1H), 7.80 – 7.73 (m, 2H), 7.45 – 7.32 (m, 4H), 7.32 – 7.27 (m, 3H), 7.19 (s, 1H), 4.87 – 4.73 (m, 2H), 3.77 (s, 3H), 2.13 – 1.99 (m, 2H), 1.97 (s, 3H), 0.90 – 0.78 (m, 1H), 0.51 – 0.36 (m, 2H), 0.10 – 0.03 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.5, 159.3, 137.1, 136.2, 135.4, 134.8, 134.3, 129.6, 128.9, 128.8, 128.3, 127.5, 75.3, 52.1, 43.2, 20.8, 6.0, 4.9, 4.9

methyl (R,Z)-3-(acetoxymethyl)-2-((chlorobenzylidene)amino)-2-phenethyl-4-phenylbut-3-enoate
Identifier	5ar
Z:E ratio	>20:1
HPLC	91 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 230 nm); tr = 27.00 and 30.00 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.15 (m, 14H), 7.13 (s, 1H), 4.91 – 4.63 (m, 2H), 3.77 (s, 3H), 3.72 – 3.44 (m, 2H), 2.77 – 2.65 (m, 1H), 2.60 – 2.48 (m, 1H), 2.43 – 2.23 (m, 2H), 2.00 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.1, 170.5, 141.7, 138.6, 135.9, 134.8, 134.6, 132.8, 129.5, 128.7, 128.5, 128.5, 128.4, 127.7, 126.0, 68.2, 60.9, 52.3, 46.3, 34.3, 29.9, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2,4-diphenylbut-3-enoate
Identifier	5as
Z:E ratio	>20:1
HPLC	86 % ee (Chiralcel OD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 7.76 and 9.80 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.15 (s, 1H), 7.81 – 7.73 (m, 2H), 7.48 – 7.24 (m, 12H), 6.95 (s, 1H), 4.92 (d, J = 12.5 Hz, 1H), 4.77 (d, J = 12.5 Hz, 1H), 3.82 (s, 3H), 1.77 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.8, 170.3, 162.9, 140.0, 137.3, 136.9, 136.3, 136.1, 134.7, 129.9, 129.1, 128.9, 128.8, 128.3, 128.2, 127.9, 127.6, 80.0, 61.6, 52.9, 20.6

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)pent-4-enoate
Identifier	5at
Z:E ratio	>20:1
HPLC	93 % ee (Chiralcel IA, i-propanol/hexane = 3/97, flow rate 0.7 mL/min, λ = 250 nm); tr = 25.14 and 27.82 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.21 (s, 1H), 7.80 – 7.72 (m, 2H), 7.46 – 7.38 (m, 2H), 7.38 – 7.32 (m, 2H), 7.32 – 7.26 (m, 3H), 7.16 (s, 1H), 5.93 – 5.78 (m, 2H), 5.14 – 5.04 (m, 2H), 3.76 (s, 3H), 3.20 – 2.72 (m, 2H), 2.00 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.4, 170.5, 159.7, 137.3, 136.2, 134.8, 134.7, 134.6, 132.8, 129.7, 128.9, 128.8, 128.3, 127.6, 118.8, 74.6, 61.4, 52.3, 42.2, 20.8

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)oct-7-enoate
Identifier	5au
Z:E ratio	>20:1
HPLC	92 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 7.40 and 9.87 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.80 – 7.72 (m, 2H), 7.47 – 7.33 (m, 4H), 7.32 – 7.27 (m, 3H), 7.20 (s, 1H), 5.84 – 5.69 (m, 1H), 5.08 – 4.87 (m, 2H), 4.84 – 4.70 (m, 2H), 3.75 (s, 3H), 2.20 – 2.02 (m, 4H), 2.00 (s, 3H), 1.47 – 1.34 (m, 4H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.4, 158.9, 138.6, 137.2, 136.3, 134.9, 134.7, 134.6, 129.6, 128.9, 128.8, 128.3, 127.5, 114.4, 61.4, 52.2, 37.7, 33.5, 29.2, 22.9, 20.8

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)hex-4-ynoate
Identifier	5av
Z:E ratio	>20:1
HPLC	92 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 12.45 and 17.18 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.32 (s, 1H), 7.78 (d, J = 8.5 Hz, 2H), 7.46 – 7.33 (m, 4H), 7.32 – 7.26 (m, 3H), 7.17 (s, 1H), 4.92 – 4.80 (m, 2H), 3.78 (s, 3H), 3.14 – 3.04 (m, 1H), 2.99 – 2.88 (m, 1H), 1.99 (s, 3H), 1.73 (t, J = 2.5 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.9, 170.4, 160.4, 137.2, 136.1, 135.2, 134.6, 134.5, 129.8, 128.9, 128.8, 128.3, 127.6, 79.3, 74.2, 74.2, 61.2, 52.5, 28.0, 20.8, 3.5

methyl (R,E)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)-5-phenylpent-4-enoate
Identifier	5aw
Z:E ratio	>20:1
HPLC	85 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 0.7 mL/min, λ = 250 nm); tr = 11.89 and 15.08 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.22 (s, 1H), 7.79 – 7.72 (m, 2H), 7.44 – 7.37 (m, 2H), 7.41 – 7.30 (m, 2H), 7.32 – 7.22 (m, 7H), 7.25 – 7.15 (m, 2H), 6.48 – 6.39 (m, 1H), 6.30 – 6.18 (m, 1H), 4.93 – 4.79 (m, 2H), 3.78 (s, 3H), 3.15 – 3.05 (m, 1H), 3.03 – 2.93 (m, 1H), 2.01 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.4, 170.4, 159.8, 137.4, 137.2, 136.1, 134.9, 134.8, 134.5, 134.0, 129.7, 128.9, 128.8, 128.4, 128.3, 127.6, 127.2, 126.1, 124.6, 75.1, 61.4, 52.3, 41.5, 20.8

methyl (S,Z)-3-(acetoxymethyl)-2-(tert-butoxymethyl)-2-((4-chlorobenzylidene)amino)-4-phenylbut-3-enoate
Identifier	5ax
Z:E ratio	>20:1
HPLC	92 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 9.46 and 16.98 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.27 (s, 1H), 7.75 (d, J = 8.5 Hz, 2H), 7.45 – 7.33 (m, 4H), 7.32 – 7.27 (m, 3H), 7.16 (s, 1H), 4.84 – 4.73 (m, 2H), 3.75 (s, 3H), 3.56 – 3.41 (m, 2H), 2.52 – 2.41 (m, 1H), 2.38 – 2.27 (m, 1H), 1.99 (s, 3H), 1.13 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.5, 170.4, 159.7, 137.2, 136.1, 135.0, 134.6, 134.4, 129.6, 128.9, 128.8, 128.3, 127.6, 73.3, 72.9, 61.4, 57.1, 52.2, 38.6, 27.4, 20.8

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)-5-methoxypentanoate
Identifier	5ay
Z:E ratio	>20:1
HPLC	90 % ee (Chiralcel AS-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 270 nm); tr = 11.34 and 13.13 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.38 – 7.32 (m, 2H), 7.31 – 7.27 (m, 3H), 7.21 (s, 1H), 4.83 – 4.72 (m, 2H), 3.75 (s, 3H), 3.43 – 3.30 (m, 2H), 3.28 (s, 3H), 2.16 (dp, J = 9.7, 7.4 Hz, 2H), 2.00 (s, 3H), 1.76 – 1.62 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.8, 170.5, 159.1, 137.2, 136.2, 134.8, 134.7, 134.6, 129.7, 128.9, 128.8, 128.3, 127.5, 74.7, 72.7, 61.4, 58.5, 52.3, 34.5, 23.9, 20.8

methyl (R,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-(2-(methylthio)ethyl)-4-phenylbut-3-enoate
Identifier	5az
Z:E ratio	>20:1
HPLC	91 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 0.7 mL/min, λ = 250 nm); tr = 14.69 and 17.53 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.19 (s, 1H), 7.79 – 7.72 (m, 2H), 7.46 – 7.40 (m, 2H), 7.39 – 7.32 (m, 2H), 7.32 – 7.27 (m, 3H), 7.16 (s, 1H), 4.84 – 4.70 (m, 2H), 3.77 (s, 3H), 2.67 – 2.51 (m, 2H), 2.47 – 2.30 (m, 2H), 2.09 (s, 3H), 2.03 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.3, 170.5, 159.4, 137.5, 136.0, 135.2, 134.4, 134.2, 129.7, 129.0, 128.8, 128.4, 127.7, 74.9, 61.3, 52.4, 38.1, 28.6, 20.9, 15.6

dimethyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)pentanedioate
Identifier	5ba
Z:E ratio	>20:1
HPLC	93 % ee (Chiralcel IC, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 25.08 and 28.49 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.17 (s, 1H), 7.78 – 7.70 (m, 2H), 7.45 – 7.39 (m, 2H), 7.38 – 7.32 (m, 2H), 7.32 – 7.24 (m, 3H), 7.16 (s, 1H), 4.88 – 4.64 (m, 2H), 3.77 (s, 3H), 3.59 (s, 3H), 2.58 – 2.35 (m, 4H), 2.02 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.7, 172.2, 170.4, 159.6, 137.5, 135.9, 135.5, 134.4, 134.1, 129.7, 128.9, 128.8, 128.4, 127.7, 74.5, 61.3, 52.4, 51.6, 32.9, 28.9, 20.8

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-6-(((benzyloxy)carbonyl)amino)-2-((4-chlorobenzylidene)amino)hexanoate
Identifier	5bb
Z:E ratio	>20:1
HPLC	93 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 43.96 and 57.69 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.17 (s, 1H), 7.74 (d, J = 8.5 Hz, 2H), 7.44 – 7.27 (m, 12H), 7.14 (s, 1H), 5.06 (s, 2H), 4.92 – 4.83 (m, 1H), 4.82 – 4.62 (m, 2H), 3.75 (s, 3H), 3.26 – 3.17 (m, 2H), 2.13 (h, J = 7.3, 6.9 Hz, 2H), 1.99 (s, 3H), 1.70 – 1.57 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.6, 170.5, 159.5, 156.3, 137.4, 136.6, 136.0, 135.0, 134.6, 134.4, 129.7, 129.0, 128.8, 128.5, 128.4, 128.1, 127.7, 74.9, 66.6, 61.3, 52.4, 41.2, 35.1, 24.3, 20.8

methyl (R)-2-((Z)-3-acetoxy-1-phenylprop-1-en-2-yl)-2-((4-chlorobenzylidene)amino)-13-hydroxytridecanoate
Identifier	5bc
Z:E ratio	>20:1
HPLC	91 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 21.62 and 25.61 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.80 – 7.71 (m, 2H), 7.45 – 7.31 (m, 4H), 7.33 – 7.24 (m, 3H), 7.20 (s, 1H), 4.77 (s, 2H), 3.75 (s, 3H), 3.62 (t, J = 6.6 Hz, 2H), 2.17 – 2.00 (m, 2H), 1.99 (s, 3H), 1.60 – 1.48 (m, 2H), 1.43 – 1.13 (m, 16H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.5, 158.9, 137.1, 136.3, 134.9, 134.7, 134.6, 129.6, 128.9, 128.8, 128.3, 127.5, 74.9, 63.0, 61.4, 52.2, 37.9, 32.7, 29.9, 29.5, 29.4, 29.4, 29.3, 25.6, 23.5, 20.8

(Z)-2-((R)-3-((4-chlorobenzylidene)amino)-2-oxotetrahydrofuran-3-yl)-3-phenylallyl acetate
Identifier	5bd
Z:E ratio	>20:1
HPLC	95 % ee (Chiralcel AS-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 25.21 and 32.79 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.42 (s, 1H), 7.79 – 7.71 (m, 2H), 7.45 – 7.24 (m, 7H), 7.05 (s, 1H), 4.82 (s, 2H), 4.52 – 4.31 (m, 2H), 2.98 – 2.87 (m, 1H), 2.84 – 2.73 (m, 1H), 1.98 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.8, 170.3, 162.5, 137.7, 136.2, 135.2, 133.9, 132.5, 129.8, 129.0, 128.8, 128.4, 128.1, 72.9, 65.3, 60.8, 37.2, 20.8

methyl (R)-2-((4-chlorobenzylidene)amino)-2-methyl-3-methylenepent-4-enoate
Identifier	6a
Regioisomeric ratio	>20:1 rr
HPLC	98 % ee (Chiralcel OJ-H, i-propanol/hexane = 2/98, flow rate 0.7 mL/min, λ = 270 nm); tr = 18.77 and 21.62 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.11 (s, 1H), 7.74 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 6.24 (dd, J = 17.7, 11.2 Hz, 1H), 5.47 (d, J = 36.9 Hz, 2H), 5.26 (d, J = 17.6 Hz, 1H), 5.07 (d, J = 11.2 Hz, 1H), 3.75 (s, 3H), 1.64 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 173.9, 159.2, 147.0, 137.0, 135.5, 134.8, 130.9, 129.6, 129.5, 128.8, 116.5, 116.4, 71.1, 52.6, 24.9

methyl (R)-2-amino-2-methyl-3-methylenepent-4-enoate
Identifier	6a′
¹H NMR (400 MHz, Chloroform-d)	δ 6.49 – 6.00 (m, 1H), 5.54 – 5.19 (m, 3H), 5.11 (d, J = 11.1 Hz, 1H), 3.72 (s, 3H), 1.50 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.7, 135.3, 129.1, 115.8, 112.8, 77.4, 77.0, 76.7, 60.0, 52.5, 25.5

ethyl (R)-2-((4-chlorobenzylidene)amino)-2-methyl-3-methylenepent-4-enoate
Identifier	6b
Regioisomeric ratio	>20:1 rr
HPLC	97 % ee (Chiralpak OJ, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 280 nm); tr = 11.48 and 13.09 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.12 (s, 1H), 7.74 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 6.23 (dd, J = 17.7, 11.2 Hz, 1H), 5.51 (s, 1H), 5.42 (s, 1H), 5.27 (d, J = 17.7 Hz, 1H), 5.06 (d, J = 11.2 Hz, 1H), 4.29 – 4.16 (m, 2H), 1.63 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.3, 159.1, 147.1, 136.9, 135.5, 134.8, 129.6, 128.8, 116.5, 116.2, 71.0, 61.4, 24.9, 14.1

methyl (R)-2-((4-chlorobenzylidene)amino)-2-methyl-3-methylenepent-4-enoate
Identifier	6c
Regioisomeric ratio	>20:1 rr
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 2/98, flow rate 0.15 mL/min, λ = 220 nm); tr = 52.17 and 56.33 min
¹H NMR (400 MHz, Chloroform-d)	δ 6.29 (dd, J = 17.5, 11.1 Hz, 1H), 5.36 (dd, J = 17.6, 1.2 Hz, 1H), 5.26 (d, J = 14.9 Hz, 2H), 5.09 (d, J = 11.1 Hz, 1H), 5.05 – 4.93 (m, 1H), 1.48 (s, 3H), 1.22 (dd, J = 6.3, 2.1 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.6, 149.3, 135.4, 115.6, 112.6, 68.7, 59.9, 25.4, 21.5, 21.5

tert-butyl (R)-2-((4-chlorobenzylidene)amino)-2-methyl-3-methylenepent-4-enoate
Identifier	6d
Regioisomeric ratio	>20:1 rr
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 2/98, flow rate 0.15 mL/min, λ = 220 nm); tr = 43.81 and 46.33 min
¹H NMR (400 MHz, Chloroform-d)	δ 6.30 (ddd, J = 17.6, 11.2, 0.9 Hz, 1H), 5.37 (dd, J = 17.6, 1.2 Hz, 1H), 5.25 (d, J = 9.6 Hz, 2H), 5.09 (dd, J = 11.1, 1.3 Hz, 1H), 1.45 (s, 3H), 1.43 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.2, 149.5, 135.6, 115.5, 112.4, 81.2, 60.3, 27.7, 25.5

methyl (R)-2-((4-chlorobenzyl)amino)-2-ethyl-3-methylenepent-4-enoate
Identifier	6e
Regioisomeric ratio	>20:1 rr
HPLC	91 % ee (Chiralcel IA, i-propanol/hexane = 2/98, flow rate 0.3 mL/min, λ = 230 nm); tr = 19.15 and 22.38 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.28 – 7.27 (m, 4H), 6.26 (dd, J = 17.5, 11.0 Hz, 1H), 5.50 (dd, J = 17.5, 1.5 Hz, 1H), 5.47 (s, 1H), 5.26 (s, 1H), 5.08 (dd, J = 11.0, 1.5 Hz, 1H), 3.71 (s, 3H), 3.50 (d, J = 12.6 Hz, 1H), 3.41 (d, J = 12.6 Hz, 1H), 2.02 – 1.96 (m, 1H), 1.94 – 1.87 (m, 1H), 0.84 (t, J = 7.4 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 174.6, 146.2, 139.0, 135.6, 132.6, 129.6, 128.4, 115.7, 114.1, 67.9, 52.2, 45.9, 24.9, 7.6

methyl (R)-2-((4-chlorobenzylidene)amino)-3-methylene-2-propylpent-4-enoate
Identifier	6f
Regioisomeric ratio	>20:1 rr
HPLC	91 % ee (Chiralcel IA, i-propanol/hexane = 2/98, flow rate 0.3 mL/min, λ = 250 nm); tr = 19.18 and 22.38 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 7.74 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 6.18 (dd, J = 17.6, 11.2 Hz, 1H), 5.54 (s, 1H), 5.45 (s, 1H), 5.27 (d, J = 17.6 Hz, 1H), 5.04 (d, J = 11.2 Hz, 1H), 3.74 (s, 3H), 2.13 – 1.99 (m, 1H), 1.93 – 1.83 (m, 1H), 1.47 – 1.36 (m, 1H), 1.36 – 1.24 (m, 1H), 0.88 (t, J = 7.4 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.3, 159.0, 146.2, 136.9, 135.6, 134.9, 129.6, 128.8, 116.5, 116.3, 74.3, 52.3, 40.8, 17.1, 14.4

methyl (R)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)decanoate
Identifier	6g
Regioisomeric ratio	>20:1 rr
HPLC	90 % ee (Chiralpak IA, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 270 nm); tr = 4.90 and 6.72 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 7.74 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 6.18 (dd, J = 17.6, 11.2 Hz, 1H), 5.54 (s, 1H), 5.45 (s, 1H), 5.28 (d, J = 17.6 Hz, 1H), 5.04 (d, J = 11.2 Hz, 1H), 3.74 (s, 3H), 2.15 – 2.00 (m, 1H), 1.95 – 1.83 (m, 1H), 1.44 – 1.34 (m, 1H), 1.33 – 1.12 (m, 11H), 0.85 (t, J = 6.8 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.4, 159.1, 146.2, 136.9, 135.7, 134.9, 129.6, 128.8, 116.6, 116.3, 74.3, 52.3, 38.6, 31.8, 30.0, 29.3, 29.2, 23.6, 22.6, 14.1

methyl (R)-2-((4-chlorobenzylidene)amino)-3-methylene-2-phenethylpent-4-enoate
Identifier	6h
Regioisomeric ratio	>20:1 rr
HPLC	91 % ee (Chiralpak IA, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 210 nm); tr = 10.53 and 17.66 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.15 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.5 Hz, 2H), 7.25 – 7.21 (m, 2H), 7.19 – 7.10 (m, 3H), 6.23 (dd, J = 17.6, 11.1 Hz, 1H), 5.57 (s, 1H), 5.46 (s, 1H), 5.34 (d, J = 17.6 Hz, 1H), 5.09 (d, J = 11.1 Hz, 1H), 3.76 (s, 3H), 2.79 – 2.68 (m, 1H), 2.67 – 2.57 (m, 1H), 2.45 – 2.35 (m, 1H), 2.30 – 2.18 (m, 1H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.0, 159.5, 146.0, 142.1, 137.1, 135.5, 134.8, 129.7, 128.9, 128.4, 128.3, 125.8, 116.7, 116.5, 74.2, 52.4, 40.3, 30.2

methyl (S)-2-((4-chlorobenzylidene)amino)-3-methylene-2-phenylpent-4-enoate
Identifier	6i
Regioisomeric ratio	>20:1 rr
HPLC	80 % ee (Chiralcel IA, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 254 nm); tr = 8.53 and 14.14 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.20 (s, 1H), 7.83 (d, J = 8.2 Hz, 2H), 7.69 – 7.56 (m, 2H), 7.42 (d, J = 8.2 Hz, 2H), 7.40 – 7.35 (m, 2H), 7.33 – 7.30 (m, 1H), 6.09 (dd, J = 17.6, 11.1 Hz, 1H), 5.74 (s, 1H), 5.18 (s, 1H), 5.13 (d, J = 17.6 Hz, 1H), 5.00 (d, J = 11.1 Hz, 1H), 3.74 (s, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 171.9, 162.7, 146.4, 139.9, 137.2, 135.4, 134.8, 129.9, 128.8, 128.6, 128.0, 127.6, 119.0, 117.4, 79.1, 52.9

methyl (R)-2-allyl-2-((4-chlorobenzylidene)amino)-3-methylenepent-4-enoate
Identifier	6j
Regioisomeric ratio	>20:1 rr
HPLC	90 % ee (Chiralcel IA, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 244 nm); tr = 6.52 and 8.28 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.45 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 6.26 – 6.17 (m, 1H), 5.88 – 5.71 (m, 1H), 5.62 (s, 1H), 5.53 (dd, J = 17.4, 1.2 Hz, 1H), 5.43 (s, 1H), 5.29 – 5.16 (m, 2H), 5.15 (d, J = 11.0 Hz, 1H), 4.67 (d, J = 9.2 Hz, 1H), 3.72 (s, 3H), 3.19 – 3.02 (m, 1H), 2.90 – 2.72 (m, 1H), 2.45 (d, J = 9.2 Hz, 1H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.0, 144.1, 135.0, 134.1, 131.8, 129.1, 128.7, 119.9, 119.7, 116.9, 116.7, 67.2, 52.5, 47.3, 37.6

methyl (R)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)oct-7-enoate
Identifier	6k
Regioisomeric ratio	>20:1 rr
HPLC	94 % ee (Chiralpak IA, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 270 nm); tr = 6.60 and 8.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 7.74 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), 6.18 (dd, J = 17.6, 11.2 Hz, 1H), 5.88 – 5.69 (m, 1H), 5.54 (s, 1H), 5.44 (s, 1H), 5.28 (d, J = 17.6 Hz, 1H), 5.04 (d, J = 11.2 Hz, 1H), 5.00 – 4.85 (m, 2H), 3.74 (s, 3H), 2.16 – 1.86 (m, 4H), 1.53 – 1.21 (m, 4H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.3, 159.2, 146.2, 138.7, 137.0, 135.6, 134.9, 129.6, 128.8, 116.5, 116.4, 114.3, 74.3, 52.3, 38.4, 33.4, 29.2, 23.2

methyl (R)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)hex-4-ynoate
Identifier	6l
Regioisomeric ratio	>20:1 rr
HPLC	88 % ee (Chiralcel OD-H, i-propanol/hexane = 2/98, flow rate 0.6 mL/min, λ = 226 nm); tr = 12.06 and 15.67 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.19 (s, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 6.22 (dd, J = 17.5, 11.2 Hz, 1H), 5.58 (s, 1H), 5.48 (s, 1H), 5.30 (d, J = 17.5 Hz, 1H), 5.07 (d, J = 11.2 Hz, 1H), 3.77 (s, 3H), 3.04 – 2.92 (m, 1H), 2.90 – 2.83 (m, 1H), 1.71 (t, J = 2.5 Hz, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 172.4, 160.9, 145.1, 137.1, 135.2, 134.8, 129.8, 128.8, 117.4, 116.7, 79.4, 74.1, 73.8, 52.7, 28.2, 3.5

dimethyl (R)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)pentanedioate
Identifier	6m
Regioisomeric ratio	>20:1 rr
HPLC	91 % ee (Chiralpak IA, i-propanol/hexane = 3/97, flow rate 1.0 mL/min, λ = 270 nm); tr = 12.78 and 17.87 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.10 (s, 1H), 7.72 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 6.19 (dd, J = 17.6, 11.2 Hz, 1H), 5.55 (s, 1H), 5.42 (s, 1H), 5.32 (d, J = 17.6 Hz, 1H), 5.09 (d, J = 11.2 Hz, 1H), 3.75 (s, 3H), 3.60 (s, 3H), 2.50 – 2.42 (m, 2H), 2.42 – 2.31 (m, 2H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.7, 172.5, 159.9, 145.4, 137.2, 135.2, 134.5, 129.7, 128.8, 117.0, 116.6, 73.6, 52.4, 51.5, 33.0, 28.9

methyl (R)-2-((4-chlorobenzylidene)amino)-3-methylene-2-(2-(methylthio)ethyl)pent-4-enoate
Identifier	6n
Regioisomeric ratio	>20:1 rr
HPLC	94 % ee (Chiralpak IC, i-propanol/hexane = 2/98, flow rate 0.6 mL/min, λ = 280 nm); tr = 24.96 and 41.22 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.11 (s, 1H), 7.73 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 6.19 (dd, J = 17.6, 11.2 Hz, 1H), 5.55 (s, 1H), 5.41 (s, 1H), 5.31 (d, J = 17.6 Hz, 1H), 5.08 (d, J = 11.2 Hz, 1H), 3.76 (s, 3H), 2.62 – 2.48 (m, 2H), 2.41 – 2.32 (m, 1H), 2.31 – 2.21 (m, 1H), 2.07 (s, 3H)
¹³C NMR (100 MHz, Chloroform-d)	δ 172.6, 159.8, 145.5, 137.2, 135.3, 134.6, 129.7, 128.9, 116.9, 116.6, 74.1, 52.5, 38.3, 28.7, 15.5

methyl (R)-7-(((benzyloxy)carbonyl)amino)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)heptanoate
Identifier	6o
Regioisomeric ratio	>20:1 rr
HPLC	85 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 27.00 and 32.25 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 7.73 (d, J = 8.5 Hz, 2H), 7.43 – 7.28 (m, 7H), 6.17 (dd, J = 17.6, 11.2 Hz, 1H), 5.53 (s, 1H), 5.42 (s, 1H), 5.28 (d, J = 17.9 Hz, 1H), 5.16 – 4.97 (m, 3H), 4.85 – 4.49 (m, 1H), 3.73 (s, 3H), 3.22 – 3.11 (m, 2H), 2.16 – 2.03 (m, 1H), 2.01 – 1.89 (m, 1H), 1.54 – 1.28 (m, 4H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.1, 159.4, 156.3, 146.0, 137.1, 136.6, 135.5, 134.7, 129.7, 128.9, 128.8, 128.5, 128.1, 116.7, 116.4, 74.2, 66.5, 52.4, 40.7, 38.0, 30.1, 20.9

methyl (R)-2-(buta-1,3-dien-2-yl)-2-((4-chlorobenzylidene)amino)-13-hydroxytridecanoate
Identifier	6p
Regioisomeric ratio	>20:1 rr
HPLC	82 % ee (Chiralpak AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 270 nm); tr = 9.40 and 18.13 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.09 (s, 1H), 7.74 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 6.18 (dd, J = 17.6, 11.2 Hz, 1H), 5.54 (s, 1H), 5.44 (s, 1H), 5.27 (d, J = 17.6 Hz, 1H), 5.04 (d, J = 11.2 Hz, 1H), 3.74 (s, 3H), 3.62 (t, J = 6.6 Hz, 2H), 2.14 – 2.01 (m, 1H), 1.95 – 1.84 (m, 1H), 1.59 – 1.50 (m, 3H), 1.35 – 1.10 (m, 15H)
¹³C NMR (100 MHz, Chloroform-d)	δ 173.4, 159.1, 146.2, 136.9, 135.7, 134.9, 129.6, 128.8, 116.5, 116.3, 74.3, 63.0, 52.3, 38.6, 32.8, 29.9, 29.5, 29.5, 29.4, 29.3, 25.7, 23.6

(R)-3-(buta-1,3-dien-2-yl)-3-((4-chlorobenzylidene)amino)dihydrofuran-2(3H)-one
Identifier	6q
Regioisomeric ratio	>20:1 rr
HPLC	93 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 0.4 mL/min, λ = 250 nm); tr = 26.53 and 29.03 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.32 (s, 1H), 7.71 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 6.17 (dd, J = 17.7, 11.2 Hz, 1H), 5.55 (s, 1H), 5.33 (s, 1H), 5.27 (d, J = 17.6 Hz, 1H), 5.18 (d, J = 11.2 Hz, 1H), 4.51 – 4.42 (m, 1H), 4.31 – 4.20 (m, 1H), 3.02 – 2.90 (m, 1H), 2.88 – 2.78 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.2, 163.9, 143.8, 137.4, 134.4, 133.8, 129.7, 128.9, 119.3, 118.8, 72.4, 65.6, 37.8

methyl (R,E)-2-amino-2-methyl-3-methylenehex-4-enoate
Identifier	6r
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 0.2 mL/min, λ = 250 nm); tr = 47.30 and 51.61 min
¹H NMR (400 MHz, Chloroform-d)	δ 5.94 (d, J = 16.0 Hz, 1H), 5.92 – 5.79 (m, 2H), 5.19 (s, 1H), 5.12 (s, 1H), 3.71 (s, 3H), 1.75 (d, J = 6.2 Hz, 3H), 1.49 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.8, 153.7, 129.0, 127.6, 110.7, 60.1, 52.5, 25.5, 18.5

methyl (R,E)-2-amino-2-methyl-3-methyleneoct-4-enoate
Identifier	6s
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 4/96, flow rate 0.5 mL/min, λ = 250 nm); tr = 14.35 and 15.86 min
¹H NMR (400 MHz, Chloroform-d)	δ 5.90 – 5.82 (m, 1H), 5.81 – 5.69 (m, 1H), 5.12 (s, 1H), 5.07 (s, 1H), 3.64 (s, 3H), 2.03 – 1.93 (m, 2H), 1.42 (s, 3H), 1.40 – 1.27 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.7, 148.8, 132.8, 128.0, 110.6, 60.3, 52.4, 35.0, 25.4, 22.3, 13.5

methyl (R,E)-2-amino-8-chloro-2-methyl-3-methyleneoct-4-enoate
Identifier	6t
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	87 % ee (Chiralcel OD-H, i-propanol/hexane = 2/98, flow rate 1.0 mL/min, λ = 250 nm); tr = 23.50 and 28.63 min
¹H NMR (400 MHz, Chloroform-d)	δ 5.99 (d, J = 16.8 Hz, 1H), 5.86 – 5.71 (m, 1H), 5.21 (s, 1H), 5.17 (s, 1H), 3.71 (s, 3H), 3.52 (t, J = 6.6 Hz, 2H), 2.29 – 2.19 (m, 2H), 1.90 – 1.81 (m, 2H), 1.48 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.9, 149.3, 130.6, 129.4, 111.4, 71.4, 52.6, 44.2, 31.9, 30.1, 25.5

methyl (R,E)-2-amino-2-methyl-3-methylenetetradec-4-enoate
Identifier	6u
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 2/98, flow rate 0.15 mL/min, λ = 250 nm); tr = 49.59 and 53.47 min
¹H NMR (400 MHz, Chloroform-d)	δ 5.92 (d, J = 15.8 Hz, 1H), 5.87 – 5.77 (m, 1H), 5.19 (s, 1H), 5.14 (s, 1H), 3.70 (s, 3H), 2.11 – 2.03 (m, 2H), 1.49 (s, 3H), 1.42 – 1.33 (m, 2H), 1.33 – 1.18 (m, 13H), 0.88 (t, J = 6.8 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.8, 148.9, 133.2, 127.8, 110.6, 60.3, 52.5, 33.1, 31.9, 29.5, 29.5, 29.3, 29.2, 29.1, 25.5, 22.7, 14.1

methyl (R,E)-2-amino-6-((tert-butyldimethylsilyl)oxy)-2-methyl-3-methylenehex-4-enoate
Identifier	6v
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 3/97, flow rate 0.4 mL/min, λ = 240 nm); tr = 18.58 and 21.58 min
¹H NMR (400 MHz, Chloroform-d)	δ 6.09 (d, J = 15.4 Hz, 1H), 5.91 – 5.80 (m, 1H), 5.19 (s, 1H), 5.14 (s, 1H), 4.14 (dd, J = 4.8, 1.9 Hz, 2H), 3.63 (s, 3H), 1.42 (s, 3H), 0.84 (s, 9H), −0.00 (s, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.5, 148.3, 131.1, 127.2, 111.7, 63.5, 60.4, 52.5, 25.9, 25.5, 18.3, −5.2

methyl (R,E)-2-amino-7-(benzyloxy)-2-methyl-3-methylenehept-4-enoate
Identifier	6w
Regioisomeric ratio	2:1 rr
Z:E ratio	>20:1
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 250 nm); tr = 25.21 and 29.60 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.27 (m, 5H), 6.09 – 5.95 (m, 1H), 5.94 – 5.80 (m, 1H), 5.21 (s, 1H), 5.16 (s, 1H), 4.51 (s, 2H), 3.68 (s, 3H), 3.51 (t, J = 6.7 Hz, 2H), 2.45 – 2.35 (m, 2H), 1.48 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.7, 148.7, 138.4, 129.7, 129.0, 128.4, 127.6, 127.6, 111.3, 72.9, 69.6, 60.3, 52.5, 33.5, 25.5

(R)-3a, scale-up reaction
Identifier	3a
HPLC	99 % ee

For (R)-4a; desired product (R)-3a, scale-up reaction
HPLC	95 % ee

(R)-5a, scale-up reaction
Identifier	5a
HPLC	97 % ee

(R)-6a, scale-up reaction
Identifier	6a
HPLC	96 % ee

methyl (S,Z)-3-(acetoxymethyl)-2-((4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	(S,Z)-5a
Z:E ratio	>20:1
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 4/96, flow rate 1.0 mL/min, λ = 230 nm); tr = 15.32 and 23.44 min
¹H and ¹³C NMR	(S,Z)-5a and (R,Z)-5a are enantiomers; consequently, their spectra are identical

methyl (R,E)-3-(acetoxymethyl)-2-((-4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	(R,E)-5a
HPLC	97 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 16.14 and 19.63 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.11 (s, 1H), 7.59 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 7.30 – 7.24 (m, 2H), 7.23 – 7.15 (m, 3H), 6.89 (s, 1H), 5.04 (d, J = 13.3 Hz, 1H), 4.87 (d, J = 13.3 Hz, 1H), 3.29 (s, 3H), 2.08 (s, 3H), 1.69 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.4, 170.5, 158.3, 137.1, 137.1, 136.5, 134.5, 131.6, 129.6, 128.8, 128.5, 127.9, 127.1, 70.6, 67.0, 51.9, 25.9, 21.1

methyl (S,E)-3-(acetoxymethyl)-2-((-4-chlorobenzylidene)amino)-2-methyl-4-phenylbut-3-enoate
Identifier	(S,E)-5a
HPLC	98 % ee (Chiralcel IC, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 16.14 and 19.63 min
¹H and ¹³C NMR	(S,E)-5a and (R,E)-5a are enantiomers; consequently, their spectra are identical

methyl (R)-2-methyl-5-phenyl-2,3-dihydro-1H-pyrrole-2-carboxylate
Identifier	8
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 11.32 and 13.88 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.87 (d, J = 6.5 Hz, 2H), 7.50 – 7.36 (m, 3H), 3.74 (s, 3H), 3.20 – 3.01 (m, 2H), 2.57 – 2.45 (m, 1H), 2.01 – 1.89 (m, 1H), 1.58 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.3, 173.9, 134.0, 130.9, 128.4, 128.0, 79.7, 52.4, 35.5, 33.9, 25.2

methyl (R)-2-((S)-2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-phenylpropanamido)-2-methyl-5-phenylpent-4-ynoate
Identifier	9
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 21.62 and 25.61 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.75 (d, J = 7.3 Hz, 2H), 7.53 – 7.42 (m, 2H), 7.42 – 7.36 (m, 2H), 7.33 – 7.17 (m, 12H), 6.57 (brs, 1H), 5.36 (brs, 1H), 4.54 – 4.31 (m, 2H), 4.23 – 4.05 (m, 2H), 3.77 (s, 3H), 3.33 – 2.95 (m, 4H), 1.58 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 170.1, 143.6, 141.3, 131.6, 129.4, 128.6, 128.2, 128.0, 127.7, 127.1, 127.0, 125.1, 125.0, 122.9, 119.9, 84.2, 83.6, 67.0, 59.1, 52.9, 47.0, 27.5, 22.6

methyl (R)-2-methyl-2-((4-methylphenyl)sulfonamido)-5-phenylpentanoate
Identifier	10
¹H NMR (400 MHz, Chloroform-d)	δ 7.79 – 7.71 (m, 2H), 7.31 – 7.26 (m, 3H), 7.06 – 6.97 (m, 2H), 7.01 – 6.88 (m, 2H), 5.43 (s, 1H), 3.64 (s, 3H), 2.53 – 2.34 (m, 5H), 1.98 – 1.86 (m, 1H), 1.79 – 1.65 (m, 1H), 1.61 (s, 1H), 1.60 – 1.48 (m, 1H), 1.40 (s, 3H), 1.39 – 1.23 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.0, 162.5, 160.0, 143.2, 139.6, 137.1, 137.1, 129.6, 129.5, 127.0, 115.1, 114.9, 62.5, 52.9, 38.7, 34.6, 25.6, 22.8, 21.5

(R)-N-(1-hydroxy-2-methyl-5-phenylpent-4-yn-2-yl)-4-methylbenzenesulfonamide
Identifier	11
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 254 nm); tr = 11.15 and 16.49 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.66 (d, J = 8.0 Hz, 2H), 7.30 – 7.15 (m, 7H), 5.04 (s, 1H), 5.00 – 4.89 (m, 2H), 3.70 (d, J = 11.7 Hz, 1H), 3.51 (d, J = 11.6 Hz, 1H), 2.33 (s, 3H), 1.22 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 206.9, 143.3, 139.3, 134.2, 129.5, 129.2, 128.2, 127.5, 127.2, 108.5, 78.9, 67.7, 60.9, 21.8, 21.5

methyl (R)-2-(3-butylureido)-2-methyl-5-phenylpent-4-ynoate
Identifier	12
HPLC	99 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 16.00 and 21.39 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 2H), 7.31 – 7.24 (m, 3H), 5.39 (s, 1H), 4.79 (t, J = 5.7 Hz, 1H), 3.76 (s, 3H), 3.23 – 3.10 (m, 4H), 1.62 (s, 3H), 1.53 – 1.38 (m, 2H), 1.37 – 1.24 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.6, 157.1, 131.7, 131.6, 128.2, 127.9, 123.5, 85.6, 83.2, 58.6, 52.7, 40.2, 32.2, 28.4, 23.6, 19.9, 13.7

methyl (R)-2-methyl-5-oxo-5-phenyl-2-(thiophene-2-carboxamido)pentanoate
Identifier	13
HPLC	99 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 21.23 and 25.03 min
¹H NMR (400 MHz, Chloroform-d)	δ 8.02 – 7.89 (m, 2H), 7.61 – 7.52 (m, 3H), 7.50 – 7.41 (m, 3H), 7.11 – 7.03 (m, 1H), 3.79 (s, 3H), 3.25 – 3.13 (m, 1H), 3.09 – 2.94 (m, 1H), 2.73 – 2.62 (m, 1H), 2.40 – 2.29 (m, 1H), 1.76 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 200.2, 174.4, 161.1, 139.3, 136.4, 133.4, 130.2, 128.6, 128.1, 127.6, 59.9, 52.9, 33.8, 31.6, 23.3

methyl (R)-2-(3-butylureido)-2-methyl-3-phenylpenta-3,4-dienoate
Identifier	15
HPLC	95 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 1.0 mL/min, λ = 254 nm); tr = 34.57 and 44.06 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.31 – 7.17 (m, 5H), 5.54 (s, 1H), 5.28 – 5.16 (m, 2H), 4.50 (t, J = 5.7 Hz, 1H), 3.73 (s, 3H), 3.17 – 2.99 (m, 2H), 1.83 (s, 3H), 1.47 – 1.33 (m, 2H), 1.32 – 1.17 (m, 2H), 0.87 (t, J = 7.2 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.5, 174.5, 156.3, 134.2, 128.2, 128.0, 127.3, 108.0, 79.8, 60.1, 53.1, 40.0, 32.1, 24.4, 19.9, 13.7

methyl (R)-2-((S)-2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-phenylpropanamido)-2-methyl-3-phenylpenta-3,4-dienoate
Identifier	16
Diastereomeric ratio	>20:1 (¹H NMR)
¹H NMR (400 MHz, Chloroform-d)	δ 7.75 (d, J = 7.5 Hz, 2H), 7.55 – 7.47 (m, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.34 – 7.27 (m, 4H), 7.25 – 7.18 (m, 4H), 7.17 – 7.01 (m, 4H), 6.88 (s, 1H), 5.37 – 5.10 (m, 3H), 4.47 – 4.07 (m, 4H), 3.74 (s, 3H), 3.07 – 2.59 (m, 2H), 1.78 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 208.5, 173.6, 169.4, 155.7, 143.8, 141.3, 136.3, 133.9, 129.3, 128.6, 128.4, 127.9, 127.7, 127.6, 127.1, 126.9, 125.1, 125.1, 120.0, 107.2, 80.4, 67.1, 60.1, 56.0, 53.3, 47.1, 38.3, 23.2

methyl (R)-2-methyl-3-phenyl-1-tosyl-2,5-dihydro-1H-pyrrole-2-carboxylate
Identifier	17
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 15/85, flow rate 1.0 mL/min, λ = 254 nm); tr = 16.46 and 19.60 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.81 – 7.74 (m, 2H), 7.36 – 7.28 (m, 5H), 7.25 – 7.16 (m, 2H), 6.03 (t, J = 2.2 Hz, 1H), 4.49 (dd, J = 13.9, 2.2 Hz, 1H), 4.24 (dd, J = 13.9, 2.3 Hz, 1H), 3.72 (s, 3H), 2.42 (s, 3H), 1.74 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.7, 143.4, 143.2, 137.8, 132.6, 129.6, 128.6, 128.4, 127.2, 126.9, 123.1, 74.9, 54.2, 52.8, 22.2, 21.5

methyl (R)-2-methyl-2-((4-methylphenyl)sulfonamido)-3-oxo-3-phenylpropanoate
Identifier	18
HPLC	97 % ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 254 nm); tr = 24.27 and 31.77 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.85 (d, J = 7.2 Hz, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.58 – 7.50 (m, 1H), 7.43 – 7.35 (m, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.33 (s, 1H), 3.61 (s, 3H), 2.38 (s, 3H), 1.76 (s, 3H), 1.59 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 191.4, 170.4, 143.5, 138.7, 133.4, 129.4, 129.1, 128.6, 127.0, 67.8, 53.6, 22.4, 21.4

(R)-N-(1-hydroxy-2-methyl-3-phenylpenta-3,4-dien-2-yl)-4-methylbenzenesulfonamide
Identifier	19
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 250 nm); tr = 10.25 and 15.42 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.75 (d, J = 8.4 Hz, 2H), 7.29 – 7.27 (m, 5H), 7.21 (d, J = 8.0 Hz, 2H), 5.50 – 4.79 (m, 2H), 4.47 (d, J = 8.8 Hz, 1H), 4.08 (d, J = 8.7 Hz, 1H), 2.40 (s, 3H), 1.95 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 206.9, 143.4, 139.3, 134.2, 129.7, 129.5, 129.2, 128.4, 128.3, 127.6, 127.2, 127.1, 127.0, 108.6, 78.9, 67.7, 61.0, 21.8, 21.5

(R,Z)-N-(4-benzylidene-3-methyl-2-oxotetrahydrofuran-3-yl)acetamide
Identifier	20
HPLC	96 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 20.08 and 34.95 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.40 – 7.33 (m, 2H), 7.30 – 7.27 (m, 1H), 7.14 (d, J = 7.2 Hz, 2H), 6.73 (s, 1H), 6.46 – 6.39 (m, 1H), 5.46 (dd, J = 14.0, 2.6 Hz, 1H), 5.24 (dd, J = 14.0, 2.7 Hz, 1H), 2.00 (s, 3H), 1.58 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.6, 169.6, 137.8, 135.2, 128.7, 128.3, 127.7, 122.8, 70.0, 57.1, 24.9, 22.2

methyl (R,Z)-3-(acetoxymethyl)-2-(2-((tert-butoxycarbonyl)amino)acetamido)-2-methyl-4-phenylbut-3-enoate
Identifier	21
HPLC	97 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 250 nm); tr = 13.16 and 18.33 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.43 – 7.12 (m, 5H), 7.02 (s, 1H), 5.18 (s, 1H), 4.80 (d, J = 12.7 Hz, 1H), 4.67 (d, J = 12.7 Hz, 1H), 4.00 – 3.66 (m, 5H), 2.01 (s, 3H), 1.91 (s, 3H), 1.46 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.65, 170.54, 168.26, 135.92, 134.36, 133.93, 128.89, 128.31, 127.74, 62.13, 60.64, 53.27, 28.30, 21.96, 20.81

(R,Z)-2-amino-3-benzylidene-2-methylbutane-1,4-diol
Identifier	22
¹H NMR (400 MHz, Chloroform-d)	δ 7.79 – 7.72 (m, 2H), 7.38 – 7.27 (m, 5H), 7.23 (d, J = 8.1 Hz, 2H), 6.84 (s, 1H), 5.78 – 5.71 (m, 1H), 4.28 – 4.18 (m, 1H), 4.06 (dd, J = 11.6, 3.3 Hz, 1H), 3.83 – 3.74 (m, 1H), 3.74 – 3.65 (m, 1H), 3.65 – 3.56 (m, 1H), 2.93 – 2.85 (m, 1H), 2.37 (s, 3H), 1.40 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 143.3, 140.7, 139.6, 136.3, 133.7, 129.5, 128.9, 128.3, 127.6, 127.1, 70.0, 63.2, 57.7, 21.8, 21.5

(R)-4-methyl-N-(4-methyl-5-oxonona-1,8-dien-4-yl)benzenesulfonamide
Identifier	23
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 254 nm); tr = 21.76 and 26.21 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.57 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.13 (s, 1H), 5.72 – 5.54 (m, 2H), 5.39 (d, J = 27.6 Hz, 2H), 5.01 – 4.83 (m, 3H), 4.67 (d, J = 11.2 Hz, 1H), 2.53 – 2.05 (m, 7H), 1.61 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 206.8, 143.0, 142.8, 139.2, 136.4, 134.0, 129.1, 127.3, 118.3, 116.5, 115.7, 67.9, 34.2, 27.9, 22.7, 21.5

(R)-N-(1-hydroxy-2-methyl-3-methylenepent-4-en-2-yl)-4-methylbenzenesulfonamide
Identifier	24
HPLC	96 % ee (Chiralcel AS-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 230 nm); tr = 41.38 and 44.50 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.75 (d, J = 8.3 Hz, 2H), 7.29 – 7.26 (m, 2H), 6.23 (dd, J = 17.1, 10.8 Hz, 1H), 5.39 (dd, J = 17.1, 1.8 Hz, 1H), 5.33 (s, 1H), 5.11 (d, J = 2.9 Hz, 2H), 5.04 (dd, J = 10.8, 1.8 Hz, 1H), 3.77 – 3.68 (m, 1H), 3.53 – 3.44 (m, 1H), 2.42 (s, 3H), 2.16 – 2.12 (m, 1H), 1.29 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 148.2, 143.2, 139.5, 134.5, 129.5, 127.1, 117.0, 113.2, 67.9, 62.4, 21.5, 21.3

methyl (R)-2-((S)-2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-phenylpropanamido)-2-methyl-3-methylenepent-4-enoate
Identifier	25
Diastereomeric ratio	>20:1 (¹H NMR)
¹H NMR (400 MHz, Chloroform-d)	δ 7.75 (d, J = 7.5 Hz, 2H), 7.56 – 7.49 (m, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.29 (t, J = 7.6 Hz, 4H), 7.24 – 7.17 (m, 2H), 6.86 (s, 1H), 6.19 – 5.89 (m, 1H), 5.53 – 5.35 (m, 2H), 5.32 – 5.19 (m, 1H), 5.17 (s, 1H), 5.03 – 4.92 (m, 1H), 4.53 – 4.24 (m, 3H), 4.22 – 4.13 (m, 1H), 3.69 (s, 3H), 3.06 (dd, J = 28.2, 10.3 Hz, 2H), 1.73 (s, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.9, 169.3, 155.8, 144.5, 143.6, 141.2, 136.3, 134.2, 129.3, 128.6, 127.6, 127.0, 126.9, 124.9, 119.9, 116.6, 115.1, 67.0, 61.9, 56.1, 53.1, 47.0, 38.3, 21.5

dimethyl (R)-4-(1-methoxy-2-((4-methylphenyl)sulfonamido)-1-oxopropan-2-yl)cyclohexa-1,4-diene-1,2-dicarboxylate
Identifier	26
HPLC	97 % ee (Chiralcel IA, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 230 nm); tr = 21.38 and 35.41 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.63 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.5 Hz, 2H), 5.89 – 5.83 (m, 2H), 3.77 (s, 3H), 3.71 (s, 3H), 3.69 (s, 3H), 3.10 – 2.85 (m, 2H), 2.42 – 2.35 (m, 2H), 2.34 (s, 3H), 1.76 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.8, 168.4, 166.8, 143.5, 138.4, 132.9, 130.2, 129.6, 129.4, 127.0, 121.7, 64.1, 53.6, 52.3, 52.1, 28.8, 26.4, 22.2, 21.4

diethyl (R)-4-(1-methoxy-2-((4-methylphenyl)sulfonamido)-1-oxopropan-2-yl)-3,6-dihydropyridazine-1,2-dicarboxylate
Identifier	27
HPLC	95 % ee (Chiralcel IA, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 230 nm); tr = 30.19 and 42.01 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.74 – 7.65 (m, 2H), 7.30 – 7.22 (m, 2H), 5.90 – 5.64 (m, 2H), 4.47 – 4.01 (m, 6H), 3.96 – 3.16 (m, 5H), 2.40 (s, 3H), 1.65 (s, 3H), 1.36 – 1.19 (m, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.3, 171.9, 155.0, 143.4, 138.9, 134.1, 133.3, 129.5, 129.5, 127.0, 121.9, 63.7, 62.5, 62.4, 53.6, 53.5, 43.9, 42.8, 21.5, 21.4, 14.6, 14.5

methyl (R)-2-((4-methylphenyl)sulfonamido)-2-(2-phenyl-3,6-dihydro-2H-1,2-oxazin-5-yl)propanoate
Identifier	28
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate 1.0 mL/min, λ = 254 nm); tr = 25.51 and 33.25 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.72 (d, J = 8.4 Hz, 2H), 7.33 – 7.21 (m, 4H), 7.05 – 6.95 (m, 3H), 6.03 – 5.94 (m, 1H), 5.76 (s, 1H), 4.34 – 4.16 (m, 2H), 3.78 – 3.73 (m, 2H), 3.71 (s, 3H), 2.34 (s, 3H), 1.70 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.3, 149.9, 143.4, 138.9, 135.5, 129.5, 128.8, 127.2, 122.5, 121.8, 115.7, 67.9, 62.9, 53.5, 51.8, 21.6, 21.4

methyl (R)-2-amino-2-methylhex-4-ynoate
Identifier	29
GC	99 % ee (BETA-DEX-375, N₂ flow rate 1.0 mL/min); tr = 26.10 and 26.70 min
¹H NMR (400 MHz, Chloroform-d)	δ 3.74 (s, 3H), 2.61 (dq, J = 16.2, 2.5 Hz, 1H), 2.39 (dq, J = 16.2, 2.5 Hz, 1H), 1.78 (t, J = 2.5 Hz, 3H), 1.35 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.9, 78.8, 74.2, 57.6, 52.4, 31.4, 25.9, 3.5

(R)-2-amino-2-methylhex-4-yn-1-ol
Identifier	30
¹H NMR (400 MHz, Chloroform-d)	δ 4.21 (brs, 3H), 3.67 – 3.32 (m, 2H), 2.55 – 2.23 (m, 2H), 1.81 (t, J = 2.5 Hz, 3H), 1.26 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 79.3, 74.2, 67.8, 54.9, 28.9, 22.9, 3.6

(R)-2-amino-2-methylhexan-1-ol
Identifier	31
¹H NMR (400 MHz, Chloroform-d)	δ 6.30 (brs, 2H), 3.85 – 3.38 (m, 2H), 1.72 (brs, 2H), 1.46 – 1.06 (m, 7H), 0.98 – 0.87 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 65.7, 58.5, 35.6, 25.4, 22.9, 20.3, 13.9

ethyl (R)-2-amino-2-(3-phenylprop-2-yn-1-yl)hexanoate
Identifier	32
HPLC	98 % ee (Chiralcel OD-H, i-propanol/hexane = 10/90, flow rate 1.0 mL/min, λ = 240 nm); tr = 8.92 and 15.98 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.42 – 7.33 (m, 2H), 7.31 – 7.26 (m, 3H), 4.34 – 4.11 (m, 2H), 2.90 (d, J = 16.5 Hz, 1H), 2.66 (d, J = 16.5 Hz, 1H), 1.84 – 1.76 (m, 1H), 1.70 – 1.58 (m, 1H), 1.45 – 1.24 (m, 6H), 1.35 – 1.10 (m, 1H), 0.91 (t, J = 7.1 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.8, 131.6, 128.2, 127.9, 123.2, 85.1, 83.4, 61.2, 60.9, 39.2, 30.9, 26.2, 22.8, 14.3, 13.9

ethyl (R)-2-butyl-5-phenyl-3,4-dihydro-2H-pyrrole-2-carboxylate
Identifier	33
HPLC	98 % ee (Chiralcel AD-H, i-propanol/hexane = 4/96, flow rate 0.7 mL/min, λ = 254 nm); tr = 8.04 and 9.38 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.92 – 7.81 (m, 2H), 7.48 – 7.36 (m, 3H), 4.32 – 4.11 (m, 2H), 3.15 – 2.94 (m, 2H), 2.54 – 2.43 (m, 1H), 2.05 – 1.88 (m, 3H), 1.45 – 1.18 (m, 7H), 0.93 – 0.86 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.4, 173.6, 134.2, 130.7, 128.3, 127.9, 83.6, 60.9, 38.6, 35.5, 31.2, 26.4, 22.9, 14.2, 13.9

tert-butyl (R)-2-amino-2-methyl-3-methylenepent-4-enoate
Identifier	34
Enantiomeric excess	96 %

tert-butyl (R)-2-acetamido-2-methyl-3-methylenepent-4-enoate
Identifier	35
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 5/95, flow rate 1.0 mL/min, λ = 254 nm); tr = 29.09 and 35.26 min
¹H NMR (400 MHz, Chloroform-d)	δ 6.68 (brs, 1H), 6.21 (dd, J = 17.6, 11.2 Hz, 1H), 5.40 (s, 1H), 5.38 – 5.30 (m, 1H), 5.25 (s, 1H), 5.04 (d, J = 11.0 Hz, 1H), 1.95 (s, 3H), 1.77 (s, 3H), 1.42 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.5, 168.6, 145.2, 135.1, 115.8, 115.2, 82.7, 61.9, 27.6, 24.0, 21.6

dimethyl (R)-4-(2-acetamido-1-(tert-butoxy)-1-oxopropan-2-yl)phthalate
Identifier	36
HPLC	96 % ee (Chiralcel AD-H, i-propanol/hexane = 10/90, flow rate 0.7 mL/min, λ = 254 nm); tr = 19.87 and 28.97 min
¹H NMR (400 MHz, Chloroform-d)	δ 7.76 (d, J = 2.0 Hz, 1H), 7.71 – 7.65 (m, 1H), 7.62 – 7.55 (m, 1H), 7.05 (brs, 1H), 3.90 (s, 3H), 3.89 (s, 3H), 2.04 (s, 3H), 2.00 (s, 3H), 1.34 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.6, 168.6, 167.9, 167.9, 144.1, 131.9, 131.0, 128.9, 128.7, 126.7, 83.5, 61.9, 52.7, 52.6, 27.5, 23.9, 21.8

(R)-1-carboxy-1-(3,4-dicarboxyphenyl)ethan-1-aminium chloride
Identifier	37
¹H NMR (400 MHz, Deuterium Oxide)	δ 7.95 – 7.90 (m, 1H), 7.87 – 7.80 (m, 1H), 7.80 – 7.73 (m, 1H), 1.97 (s, 3H)
¹³C NMR (101 MHz, D₂O)	δ 171.12, 170.7, 170.7, 139.0, 132.7, 132.1, 129.6, 129.4, 126.5, 61.7, 21.2

DPPB and [Pd(η³-allyl)Cl]₂ mixtures
³¹P NMR (THF)	Variations in the DPPB-to-Pd molar ratio led to the coexistence of two distinct species, identified as the monodentate chelate [Pd(η³-allyl)Cl]/DPPB/[Pd(η³-allyl)Cl] and the bidentate chelate Pd(κ²-DPPB)(η³-allyl)Cl; a progressive increase in the ligand loading promoted the quantitative conversion of the monodentate chelate complex [Pd(η³-allyl)Cl]/DPPB/[Pd(η³-allyl)Cl] into the corresponding bidentate chelate complex Pd(κ²-DPPB)(η³-allyl)Cl

DBFphos and [Pd(η³-allyl)Cl]₂ mixtures
³¹P NMR (THF)	Variations in the DBFphos-to-Pd molar ratio led exclusively to signals corresponding to the monodentate chelate [Pd(η³-allyl)Cl]/DBFphos/[Pd(η³-allyl)Cl] complex; increasing the ligand loading did not promote conversion to the corresponding bidentate chelate Pd(κ²-DBFphos)(η³-allyl)Cl

Xantphos and [Pd(η³-allyl)Cl]₂ mixtures
³¹P NMR (THF)	Variations in the Xantphos-to-Pd molar ratio resulted solely in signals corresponding to the bidentate chelate Pd(κ²-Xantphos)(η³-allyl)Cl; even under conditions of palladium precursor excess, no signals ascribable to the corresponding monodentate chelate [Pd(η³-allyl)Cl]/Xantphos/[Pd(η³-allyl)Cl] could be detected

Pd(I) species int-I after prolonged exposure to air during sample preparation
XPS, palladium species distribution (atomic percent)	Pd(I): 61 %; Pd(0): 2 %; Pd(II): 37 %

Pd(I) species int-I prepared with air-free techniques
XPS, palladium species distribution (atomic percent)	Pd(I): 81 %; Pd(0): 4 %; Pd(II): 15 %

Pd(II) complex
UV–Vis absorption (MeCN, µM solution; 250–500 nm)	No additional absorption at longer wavelengths

Binuclear Pd(I) complex
UV–Vis absorption (MeCN, µM solution; 250–500 nm)	Broad absorption band centered at 295 nm, significantly red-shifted relative to the intraligand transitions of the Pd(II) complex; the broad profile is characteristic of metal-metal-to-ligand charge transfer (MMLCT) or metal-ligand charge transfer (MLCT) transitions

dibenzo[b,d]furan-4-yldiphenylphosphane
Identifier	L43
¹H NMR (400 MHz, Chloroform-d)	δ 8.03 – 7.91 (m, 2H), 7.53 (d, J = 8.2 Hz, 1H), 7.46 – 7.28 (m, 13H), 7.05 – 6.90 (m, 1H)
³¹P NMR (162 MHz, CDCl₃)	δ −19.47

Initial reaction rate with different concentrations of aldimine ester 1a under propargylation reaction conditions (called propargyl carbonate 1a in the procedure)
¹⁹F NMR yield, [1a] = 0.2 mmol	60 min: –; 120 min: 4 %; 180 min: 6 %; 240 min: 10 %; 300 min: 12 %; 360 min: 16 %; 420 min: 18 %; 480 min: 20 %
¹⁹F NMR yield, [1a] = 0.4 mmol	60 min: –; 120 min: 6 %; 180 min: 11 %; 240 min: 14 %; 300 min: 18 %; 360 min: 22 %; 420 min: 25 %; 480 min: 28 %
¹⁹F NMR yield, [1a] = 0.6 mmol	60 min: –; 120 min: 7 %; 180 min: 8 %; 240 min: 12 %; 300 min: 14 %; 360 min: 20 %; 420 min: 21 %; 480 min: 22 %
¹⁹F NMR yield, [1a] = 0.8 mmol	60 min: 7 %; 120 min: 10 %; 180 min: 12 %; 240 min: 13 %; 300 min: 16 %; 360 min: 20 %; 420 min: 24 %; 480 min: 28 %
Rate dependence on the concentration of aldimine ester 1a	Zero-order

Initial reaction rate with different concentrations of propargyl carbonate 2a under propargylation reaction conditions (called aldimine ester 2a in the procedure)
¹⁹F NMR yield, [2a] = 0.2 mmol	60 min: –; 120 min: 9 %; 180 min: 11.5 %; 240 min: 14.5 %; 300 min: 20 %; 360 min: 27.5 %; 420 min: 33.5 %; 480 min: 35 %
¹⁹F NMR yield, [2a] = 0.4 mmol	60 min: –; 120 min: 6.5 %; 180 min: 8 %; 240 min: 11 %; 300 min: 16.5 %; 360 min: 23.5 %; 420 min: 29 %; 480 min: 36 %
¹⁹F NMR yield, [2a] = 0.6 mmol	60 min: –; 120 min: 10.5 %; 180 min: 12.5 %; 240 min: 18 %; 300 min: 21.5 %; 360 min: 31 %; 420 min: 32.5 %; 480 min: 39.5 %
¹⁹F NMR yield, [2a] = 0.8 mmol	60 min: 8 %; 120 min: 11.5 %; 180 min: 13.5 %; 240 min: 20 %; 300 min: 24.5 %; 360 min: 30.5 %; 420 min: 35.5 %; 480 min: not reported
Rate dependence on the concentration of propargyl carbonate 2a	Zero-order

Initial reaction rate with different concentrations of [Cu] under propargylation reaction conditions
¹⁹F NMR yield, [Cu] = 2.5 mol %	60 min: –; 120 min: 3.6 %; 180 min: 5.1 %; 240 min: 9 %; 300 min: 12.6 %; 360 min: 16.5 %; 420 min: 17.1 %
¹⁹F NMR yield, [Cu] = 5.0 mol %	60 min: –; 120 min: 5.1 %; 180 min: 7.8 %; 240 min: 12.3 %; 300 min: 17.4 %; 360 min: 21.3 %; 420 min: 26.4 %
¹⁹F NMR yield, [Cu] = 10 mol %	60 min: 3.6 %; 120 min: 6.2 %; 180 min: 9.4 %; 240 min: 13.7 %; 300 min: 18 %; 360 min: 23.7 %; 420 min: 27.9 %
¹⁹F NMR yield, [Cu] = 20 mol %	60 min: 9.4 %; 120 min: 11.7 %; 180 min: 17.4 %; 240 min: 34.0 %; 300 min: 36 %; 360 min: 43.2 %; 420 min: –
Rate dependence on [Cu]	Linear relationship in [Cu] (0.4 order)

Initial reaction rate with different concentrations of [Pd] under propargylation reaction conditions
¹⁹F NMR yield, [Pd] = 2.5 mol %	60 min: –; 120 min: 1.8 %; 180 min: 3.5 %; 240 min: 4.2 %; 300 min: 6.5 %; 330 min: –; 360 min: 10.2 %; 390 min: –; 420 min: 13.1 %
¹⁹F NMR yield, [Pd] = 5.0 mol %	60 min: –; 120 min: 2.5 %; 180 min: 7.7 %; 240 min: 9.8 %; 300 min: 15.4 %; 330 min: –; 360 min: 18.2 %; 390 min: –; 420 min: 28 %
¹⁹F NMR yield, [Pd] = 10 mol %	60 min: –; 120 min: 2.1 %; 180 min: 6.0 %; 240 min: 8.6 %; 300 min: 15.9 %; 330 min: –; 360 min: 25.3 %; 390 min: –; 420 min: 32.3 %
¹⁹F NMR yield, [Pd] = 20 mol %	60 min: –; 120 min: 3.3 %; 180 min: 8.5 %; 240 min: 14.8 %; 300 min: 23.8 %; 330 min: 26.8 %; 360 min: 34.1 %; 390 min: 43.4 %; 420 min: not reported
Rate dependence on [Pd]	Linear relationship in [Pd] (0.8 order)

Initial reaction rate with different concentrations of aldimine ester 1a under allenylation reaction conditions (called propargyl carbonate 1a in the procedure)
¹⁹F NMR yield, [1a] = 0.2 mmol	60 min: 2 %; 120 min: 3 %; 180 min: 5 %; 240 min: 7 %; 300 min: 9 %; 360 min: 10 %; 420 min: 12 %
¹⁹F NMR yield, [1a] = 0.4 mmol	60 min: 2 %; 120 min: 3 %; 180 min: 5.5 %; 240 min: 8 %; 300 min: 11 %; 360 min: 14.5 %; 420 min: 15 %
¹⁹F NMR yield, [1a] = 0.6 mmol	60 min: 2 %; 120 min: 3 %; 180 min: 4 %; 240 min: 7.5 %; 300 min: 10.5 %; 360 min: 13.5 %; 420 min: 15 %
¹⁹F NMR yield, [1a] = 0.8 mmol	60 min: 2.5 %; 120 min: 6 %; 180 min: 8.5 %; 240 min: 9.5 %; 300 min: 10.5 %; 360 min: 17 %; 420 min: –
Rate dependence on the concentration of aldimine ester 1a	Zero-order

Initial reaction rate with different concentrations of propargyl carbonate 2a under allenylation reaction conditions (called aldimine ester 2a in the procedure)
¹⁹F NMR yield, [2a] = 0.2 mmol	120 min: 3 %; 180 min: 5 %; 240 min: 9 %; 300 min: 13 %; 360 min: 15 %; 420 min: 19 %
¹⁹F NMR yield, [2a] = 0.4 mmol	120 min: 5 %; 180 min: 8 %; 240 min: 12 %; 300 min: 17 %; 360 min: 22 %; 420 min: 23 %
¹⁹F NMR yield, [2a] = 0.6 mmol	120 min: 5 %; 180 min: 6 %; 240 min: 11 %; 300 min: 16 %; 360 min: 20 %; 420 min: 23 %
¹⁹F NMR yield, [2a] = 0.8 mmol	120 min: 9 %; 180 min: 13 %; 240 min: 14 %; 300 min: 16 %; 360 min: 26 %; 420 min: –
Rate dependence on the concentration of propargyl carbonate 2a	Zero-order

Initial reaction rate with different concentrations of [Pd] under allenylation reaction conditions
¹⁹F NMR yield, [Pd] = 2.5 mol %	60 min: –; 120 min: 4.6 %; 180 min: 7.7 %; 240 min: 9.2 %; 300 min: 11.8 %; 360 min: 17.9 %
¹⁹F NMR yield, [Pd] = 5.0 mol %	60 min: 5.2 %; 120 min: 10.2 %; 180 min: 13.6 %; 240 min: 16.0 %; 300 min: 20.4 %; 360 min: 25.3 %
¹⁹F NMR yield, [Pd] = 10 mol %	60 min: 8.2 %; 120 min: 14.4 %; 180 min: 17.3 %; 240 min: 20.2 %; 300 min: 28.2 %; 360 min: 31.7 %
¹⁹F NMR yield, [Pd] = 20 mol %	60 min: 7.7 %; 120 min: 18.6 %; 180 min: 23.0 %; 240 min: 29.4 %; 300 min: –; 360 min: –
Rate dependence on [Pd]	Linear relationship in [Pd] (0.4 order)

Initial reaction rate with different concentrations of [Cu] under allenylation reaction condition
¹⁹F NMR yield, [Cu] = 2.5 mol %	60 min: 6.5 %; 120 min: 6.5 %; 180 min: 10.5 %; 240 min: 15.5 %; 300 min: 19 %; 360 min: 25.5 %; 420 min: 29 %; 480 min: 34.5 %
¹⁹F NMR yield, [Cu] = 5.0 mol %	60 min: 7.5 %; 120 min: 8 %; 180 min: 9.5 %; 240 min: 17.5 %; 300 min: 25 %; 360 min: 32.5 %; 420 min: 35 %; 480 min: 40.5 %
¹⁹F NMR yield, [Cu] = 10 mol %	60 min: 10 %; 120 min: 10 %; 180 min: 17.5 %; 240 min: 22.5 %; 300 min: 31.5 %; 360 min: 38.5 %; 420 min: 48 %; 480 min: 52 %
Rate dependence on [Cu]	Linear relationship in [Cu] (0.3 order)

tosylated ent-3d
CCDC number	2579966
Empirical formula	C₂₀H₂₀FNO₄S
Formula weight	389.43
Temperature	291.1(2) K
Crystal system	orthorhombic
Space group	P2₁2₁2₁
a	7.71124(9) Å
b	8.07978(11) Å
c	31.4622(3) Å
α	90°
β	90°
γ	90°
Volume	1960.26(4) Å³
Z	4
Calculated density	1.320 g cm⁻³
μ	1.769 mm⁻¹
F(000)	816.0
Crystal size	0.3 × 0.2 × 0.02 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	5.618 to 146.852°
Index ranges	−9 ≤ h ≤ 9, −5 ≤ k ≤ 9, −38 ≤ l ≤ 35
Reflections collected	26050
Independent reflections	3808 [Rint = 0.0276, Rsigma = 0.0152]
Data/restraints/parameters	3808/0/248
Goodness-of-fit on F²	1.070
Final R indexes [I≥2σ (I)]	R1 = 0.0303, wR2 = 0.0840
Final R indexes [all data]	R1 = 0.0317, wR2 = 0.0849
Largest diff. peak/hole	0.30/−0.29 e Å⁻³
Flack parameter	0.004(5)

acylated 4c
CCDC number	2579967
Empirical formula	C₂₇H₂₅NO₄
Formula weight	427.48
Temperature	296.66(10) K
Crystal system	triclinic
Space group	P1
a	7.5871(2) Å
b	10.9322(2) Å
c	14.9523(3) Å
α	93.014(2)°
β	98.845(2)°
γ	109.588(2)°
Volume	1147.28(5) Å³
Z	2
Calculated density	1.237 g cm⁻³
μ	0.668 mm⁻¹
F(000)	452.0
Crystal size	0.2 × 0.1 × 0.05 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	6.02 to 151.346°
Index ranges	−9 ≤ h ≤ 9, −12 ≤ k ≤ 13, −17 ≤ l ≤ 18
Reflections collected	26413
Independent reflections	7462 [Rint = 0.0211, Rsigma = 0.0188]
Data/restraints/parameters	7462/47/628
Goodness-of-fit on F²	1.054
Final R indexes [I≥2σ (I)]	R1 = 0.0359, wR2 = 0.0990
Final R indexes [all data]	R1 = 0.0407, wR2 = 0.1037
Largest diff. peak/hole	0.14/−0.12 e Å⁻³
Flack parameter	−0.03(7)

sulfonylated 5a′
CCDC number	2579968
Empirical formula	C₂₇H₂₇NO₆S
Formula weight	493.55
Temperature	297.89(10) K
Crystal system	triclinic
Space group	P1
a	10.37592(14) Å
b	10.66362(14) Å
c	12.25504(16) Å
α	108.8994(12)°
β	100.9441(11)°
γ	91.3369(11)°
Volume	1254.26(3) Å³
Z	2
Calculated density	1.307 g cm⁻³
μ	1.501 mm⁻¹
F(000)	520.0
Crystal size	0.2 × 0.15 × 0.15 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	7.796 to 151.574°
Index ranges	−13 ≤ h ≤ 12, −12 ≤ k ≤ 13, −15 ≤ l ≤ 15
Reflections collected	31968
Independent reflections	8217 [Rint = 0.0220, Rsigma = 0.0154]
Data/restraints/parameters	8217/3/637
Goodness-of-fit on F²	1.077
Final R indexes [I≥2σ (I)]	R1 = 0.0346, wR2 = 0.0977
Final R indexes [all data]	R1 = 0.0358, wR2 = 0.0988
Largest diff. peak/hole	0.17/−0.23 e Å⁻³
Flack parameter	0.017(10)

sulfonylated 6a′
CCDC number	2579969
Empirical formula	C₂₀H₂₁NO₄S
Formula weight	371.44
Temperature	295.61(10) K
Crystal system	triclinic
Space group	P1
a	8.21960(18) Å
b	10.32995(19) Å
c	22.7609(4) Å
α	91.8191(15)°
β	98.4741(17)°
γ	90.6160(16)°
Volume	1910.29(7) Å³
Z	4
Calculated density	1.291 g cm⁻³
μ	1.711 mm⁻¹
F(000)	784.0
Crystal size	0.15 × 0.1 × 0.05 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	3.928 to 152.242°
Index ranges	−10 ≤ h ≤ 10, −12 ≤ k ≤ 12, −28 ≤ l ≤ 25
Reflections collected	51004
Independent reflections	12534 [Rint = 0.0264, Rsigma = 0.0248]
Data/restraints/parameters	12534/737/1196
Goodness-of-fit on F²	1.058
Final R indexes [I≥2σ (I)]	R1 = 0.0453, wR2 = 0.1299
Final R indexes [all data]	R1 = 0.0531, wR2 = 0.1378
Largest diff. peak/hole	0.48/−0.33 e Å⁻³
Flack parameter	0.020(7)

17′
CCDC number	2579970
Empirical formula	C₂₄H₂₃NO₄S
Formula weight	421.49
Temperature	296.79(10) K
Crystal system	orthorhombic
Space group	P2₁2₁2₁
a	8.54627(13) Å
b	8.71549(14) Å
c	29.1177(4) Å
α	90°
β	90°
γ	90°
Volume	2168.83(6) Å³
Z	4
Calculated density	1.291 g cm⁻³
μ	1.574 mm⁻¹
F(000)	888.0
Crystal size	0.15 × 0.15 × 0.05 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	6.07 to 146.92°
Index ranges	−10 ≤ h ≤ 10, −10 ≤ k ≤ 10, −32 ≤ l ≤ 36
Reflections collected	33745
Independent reflections	4305 [Rint = 0.0326, Rsigma = 0.0164]
Data/restraints/parameters	4305/257/326
Goodness-of-fit on F²	1.059
Final R indexes [I≥2σ (I)]	R1 = 0.0434, wR2 = 0.1183
Final R indexes [all data]	R1 = 0.0476, wR2 = 0.1229
Largest diff. peak/hole	0.14/−0.30 e Å⁻³
Flack parameter	−0.007(8)

28
CCDC number	2579971
Empirical formula	C₂₁H₂₄N₂O₅S
Formula weight	416.48
Temperature	296.06(10) K
Crystal system	monoclinic
Space group	P2₁
a	11.1378(8) Å
b	8.5246(5) Å
c	11.2988(8) Å
α	90°
β	105.610(8)°
γ	90°
Volume	1033.20(13) Å³
Z	2
Calculated density	1.339 g cm⁻³
μ	1.692 mm⁻¹
F(000)	440.0
Crystal size	0.2 × 0.15 × 0.02 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	8.124 to 148.8°
Index ranges	−13 ≤ h ≤ 13, −10 ≤ k ≤ 6, −13 ≤ l ≤ 13
Reflections collected	13905
Independent reflections	3360 [Rint = 0.0444, Rsigma = 0.0289]
Data/restraints/parameters	3360/1/265
Goodness-of-fit on F²	1.120
Final R indexes [I≥2σ (I)]	R1 = 0.0616, wR2 = 0.1881
Final R indexes [all data]	R1 = 0.0664, wR2 = 0.1941
Largest diff. peak/hole	0.95/−0.40 e Å⁻³
Flack parameter	0.01(2)

[Pd(η³-allyl)Cl]DBFphos[Pd(η³-allyl)Cl] complex
CCDC number	2579972
Empirical formula	C₄₂H₃₆Cl₂OP₂Pd₂
Formula weight	902.35
Temperature	296.12(10) K
Crystal system	orthorhombic
Space group	Pna2₁
a	14.61561(15) Å
b	15.74243(19) Å
c	16.42634(14) Å
α	90°
β	90°
γ	90°
Volume	3779.46(7) Å³
Z	4
Calculated density	1.586 g cm⁻³
μ	10.027 mm⁻¹
F(000)	1808.0
Crystal size	0.2 × 0.1 × 0.06 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	7.778 to 147.128°
Index ranges	−17 ≤ h ≤ 18, −18 ≤ k ≤ 19, −19 ≤ l ≤ 13
Reflections collected	40737
Independent reflections	6457 [Rint = 0.0357, Rsigma = 0.0262]
Data/restraints/parameters	6457/160/461
Goodness-of-fit on F²	1.051
Final R indexes [I≥2σ (I)]	R1 = 0.0297, wR2 = 0.0817
Final R indexes [all data]	R1 = 0.0320, wR2 = 0.0834
Largest diff. peak/hole	0.79/−0.56 e Å⁻³
Flack parameter	−0.035(5)

Pd(κ²-DPPB)(η³-allyl)Cl complex
CCDC number	2579973
Empirical formula	C₃₁H₃₃ClP₂Pd
Formula weight	609.36
Temperature	200.00(10) K
Crystal system	triclinic
Space group	P1
a	9.0626(2) Å
b	12.9515(2) Å
c	23.4824(4) Å
α	89.9760(10)°
β	89.9820(10)°
γ	89.9800(10)°
Volume	2756.23(9) Å³
Z	4
Calculated density	1.468 g cm⁻³
μ	7.548 mm⁻¹
F(000)	1248.0
Crystal size	0.04 × 0.04 × 0.02 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	6.824 to 151.046°
Index ranges	−10 ≤ h ≤ 11, −16 ≤ k ≤ 14, −28 ≤ l ≤ 29
Reflections collected	39157
Independent reflections	15987 [Rint = 0.0345, Rsigma = 0.0460]
Data/restraints/parameters	15987/743/1434
Goodness-of-fit on F²	1.075
Final R indexes [I≥2σ (I)]	R1 = 0.0664, wR2 = 0.1846
Final R indexes [all data]	R1 = 0.0774, wR2 = 0.1947
Largest diff. peak/hole	1.70/−0.62 e Å⁻³

[Pd(η³-allyl)Cl]/DPPB/[Pd(η³-allyl)Cl] complex
CCDC number	2579974
Empirical formula	C₃₄H₃₈Cl₂P₂Pd₂
Formula weight	792.28
Temperature	294.77(10) K
Crystal system	triclinic
Space group	P−1
a	9.1008(3) Å
b	9.6844(3) Å
c	10.6851(3) Å
α	112.877(3)°
β	91.700(3)°
γ	90.485(3)°
Volume	867.08(5) Å³
Z	1
Calculated density	1.517 g cm⁻³
μ	10.809 mm⁻¹
F(000)	398.0
Crystal size	0.08 × 0.07 × 0.04 mm³
Radiation	Cu Kα (λ = 1.54184 Å)
2Θ range for data collection	8.988 to 151.232°
Index ranges	−11 ≤ h ≤ 11, −12 ≤ k ≤ 11, −8 ≤ l ≤ 13
Reflections collected	10994
Independent reflections	3403 [Rint = 0.0234, Rsigma = 0.0207]
Data/restraints/parameters	3403/89/209
Goodness-of-fit on F²	1.072
Final R indexes [I≥2σ (I)]	R1 = 0.0304, wR2 = 0.0817
Final R indexes [all data]	R1 = 0.0325, wR2 = 0.0834
Largest diff. peak/hole	0.66/−0.74 e Å⁻³