Compound characterization data — Krishnan et al., 2026

Chandu G. Krishnan, Luis Izquierdo Aranda, Gabriel Cormier, Nicola Michelazzo, Lilian Geniller, Stefano A. Serapian, Luca Dell’Amico. “Reprogramming phosphorus(III) chemistry via iminyl phosphines reactivity.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007677/v1

The supporting information is appended to the main paper

3-fluoro-2-((S)-4-phenyl-4,5-dihydrooxazol-2-yl)phenyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	212
¹H NMR (400 MHz, CDCl₃)	δ 7.68 – 7.54 (m, 5H), 7.51 – 7.33 (m, 10H), 7.31 – 7.25 (m, 5H), 7.22 – 7.08 (m, 6H), 7.09 – 6.95 (m, 2H), 5.18 – 5.08 (m, 1H), 4.60 – 4.52 (m, 1H), 4.23 – 4.09 (m, 2H), 3.10 – 2.95 (m, 1H), 2.38 (dd, J = 15.1, 9.7 Hz, 1H), 2.12 (br, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.2, 161.0 (d, JC-F = 253.5 Hz), 158.7, 150.1 (d, JC-F = 5.3 Hz), 145.1, 142.1, 133.1 (d, JC-P = 100.0 Hz), 132.0 (d, JC-P = 2.7 Hz), 131.9 (d, JC-P = 2.7 Hz), 131.8 (d, JC-F = 10.0 Hz), 131.7 (d, JC-P = 99.0 Hz), 131.4 (d, JC-P = 9.1 Hz), 131.3 (d, JC-P = 99.0 Hz), 130.7 (d, JC-P = 9.5 Hz), 128.8, 128.7, 128.6, 128.4 (d, JC-P = 31.2 Hz), 127.6, 126.8, 126.4, 119.5 (d, JC-F = 3.5 Hz), 113.1 (d, JC-F = 21.5 Hz), 111.3 (d, JC-F = 17.0 Hz), 74.4, 69.9, 64.3 (d, JC-P = 12.3 Hz), 48.0 (d, JC-P = 2.2 Hz), 29.6 (d, JC-P = 70.2 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.5

tert-butyl (3R)-3-amino-3-(4-chlorophenyl)-2-((diphenylphosphoryl)methyl)-3-(4-((1-isopropoxy-2-methyl-1-oxopropan-2-yl)oxy)phenyl)propanoate
Identifier	213
Sample qualifier	Mixture of diastereoisomers, d.r. = 1:1
¹H NMR (400 MHz, CDCl₃)	δ 7.77 (dd, J = 11.6, 7.4 Hz, 1H), 7.63 – 7.59 (m, 2H), 7.54 – 7.36 (m, 8H), 7.31 – 7.29 (m, 2H), 7.20 (d, J = 8.4 Hz, 1H), 7.14 (d, J = 8.3 Hz, 1H), 6.71 (d, J = 8.5 Hz, 1H), 6.66 (d, J = 8.6 Hz, 1H), 5.06 – 4.99 (m, 1H), 4.08 – 3.99 (m, 1H), 2.93 – 2.81 (m, 1H), 2.38 – 2.24 (m, 1H), 1.82 (bs, 2H), 1.55 (s, 3H), 1.50 (s, 3H), 1.18 – 1.12 (m, 6H), 0.82 – 0.81 (m, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.7 (d, JC-P = 11.0 Hz), 172.9, 154.6, 154.3, 144.6, 144.2, 138.7, 138.2, 133.8 (d, JC-P = 99.7 Hz), 133.7 (d, JC-P = 99.6 Hz), 132.7, 132.5, 132.3, 132.12 (d, JC-P = 2.8 Hz), 132.0 (d, JC-P = 2.8 Hz), 131.4 (d, JC-P = 9.4 Hz), 130.9 (d, JC-P = 9.3 Hz), 128.8 (d, JC-P = 10.5 Hz), 130.8 (d, JC-P = 9.4 Hz), 128.8 (d, JC-P = 11.6 Hz), 128.7, 128.4, 128.1, 127.8, 127.6, 127.4, 118.9, 118.4, 81.5, 81.4, 79.2, 79.1, 69.0, 63.5 (d, JC-P = 11.8 Hz), 63.4 (d, JC-P = 12.3 Hz), 46.4, 46.2, 29.2 (d, JC-P = 70.1 Hz), 27.3, 27.2, 25.7, 25.5, 25.4, 25.4, 21.7 – 21.6 (m, 2C)
³¹P NMR (162 MHz, CDCl₃)	δ 30.1
HRMS (ESI+)	Calculated for C₃₉H₄₆ClNO₆P [M+H]⁺: 690.2751; found 690.2762

(2-(2-benzamido-3-(diphenylphosphoryl)propanamido)cyclopenta-2,4-dien-1-yl)(cyclopenta-2,4-dien-1-yl)iron
Identifier	214
¹H NMR (400 MHz, CDCl₃)	δ 9.75 (s, 1H), 8.21 (d, J = 4.8 Hz, 1H), 8.00 (dd, J = 12.3, 7.2 Hz, 2H), 7.91 (d, J = 7.7 Hz, 2H), 7.73 (dd, J = 11.9, 7.6 Hz, 2H), 7.61 – 7.52 (m, 4H), 7.50 – 7.44 (m, 4H), 4.84 – 4.77 (m, 1H), 4.60 (s, 2H), 4.13 (s, 5H), 3.99 (s, 2H), 3.37 – 3.29 (m, 1H), 2.77 – 2.68 (m, 1H)
³¹P NMR (162 MHz, CDCl₃)	δ 33.3
HRMS (ESI+)	Calculated for C₃₂H₂₉FeNO₄P [M+H]⁺: 578.1172; found 578.1175

methyl 2-(((benzyloxy)carbonyl)amino)-3-(diphenylphosphorothioyl)propanoate
Identifier	215
¹H NMR (400 MHz, CDCl₃)	δ 7.83 (dd, J = 13.3, 7.2 Hz, 1H), 7.45 – 7.40 (m, 6H), 7.35 – 7.30 (m, 3H), 7.22 – 7.20 (m, 2H), 5.71 (d, J = 7.4 Hz, 1H), 4.86 – 4.71 (m, 3H), 3.66 (s, 3H), 3.39 – 3.31 (m, 1H), 3.21 – 3.13 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.1 (d, JC-P = 9.0 Hz), 155.4, 136.1, 132.9 (d, JC-P = 9.0 Hz), 132.5 (d, JC-P = 90.0 Hz), 131.8 – 131.6 (m, 2C), 131.2 (d, JC-P = 10.5 Hz), 131.0 (d, JC-P = 10.4 Hz), 128.9 (d, JC-P = 13.0 Hz), 128.7 (d, JC-P = 13.7 Hz), 128.6, 128.2, 128.1, 66.9, 52.9, 50.7, 33.1 (d, JC-P = 58.3 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 37.7
HRMS (ESI+)	Calculated for C₂₄H₂₅NO₄PS [M+H]⁺: 454.1236; found 454.1241

benzyl (1r,3r)-1-(aminodiphenylmethyl)-3-(diphenylphosphaneyl)cyclobutane-1-carboxylate
Identifier	207
¹H NMR (400 MHz, CDCl₃)	δ 7.31 – 7.22 (m, 18H), 7.21 – 7.18 (m, 5H), 7.06 – 7.04 (m, 2H), 4.99 (s, 2H), 3.08 – 2.97 (m, 1H), 2.66 – 2.60 (m, 2H), 2.52 – 2.43 (m, 2H), 2.35 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.5 (d, JC-P = 2.4 Hz), 146.5, 138.2 (d, JC-P = 14.2 Hz), 135.7, 132.82 (d, JC-P = 17.8 Hz), 135.0, 133.4, 132.2 (d, JC-P = 93.0 Hz), 132.0 (d, JC-P = 3.0 Hz), 131.1 (d, JC-P = 9.4 Hz), 128.9 (d, JC-P = 7.7 Hz), 128.8, 128.6, 67.1, 65.7, 57.0 (d, JC-P = 16.3 Hz), 33.3 (d, JC-P = 14.3 Hz), 27.1 (d, JC-P = 14.2 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ −4.8
HRMS (ESI+)	Calculated for C₃₇H₃₅NO₂P [M+H]⁺: 556.2400; found 556.2412

methyl (E)-2-((((Z)-benzylidene)amino)diphenylmethyl)-3-(diphenylphosphoryl)acrylate
Identifier	216
¹H NMR (400 MHz, CDCl₃)	δ 7.70 (s, 1H), 7.57 (dd, J = 12.0, 7.3 Hz, 4H), 7.52 – 7.38 (m, 9H), 7.36 – 7.16 (m, 12H), 6.88 (d, J = 18.2 Hz, 1H), 3.52 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.0 (d, JC-P = 20.6 Hz), 162.6, 159.2 (d, JC-P = 2.1 Hz), 142.2, 136.2, 135.2 (d, JC-P = 108.4 Hz), 131.2 (d, JC-P = 2.7 Hz), 131.0 (d, JC-P = 9.5 Hz), 130.5, 130.0, 129.2, 128.4 (d, JC-P = 12.2 Hz), 128.2 (d, JC-P = 96.6 Hz), 128.2, 127.8, 127.4, 78.1 (d, JC-P = 3.7 Hz), 52.3
³¹P NMR (162 MHz, CDCl₃)	δ 16.6
HRMS (ESI+)	Calculated for C₃₆H₃₁NO₃P [M+H]⁺: 556.2037; found 556.2128

naphthalen-1-yl acrylate
Identifier	145
¹H NMR (400 MHz, CDCl₃)	δ 7.90 – 7.88 (m, 2H), 7.77 (d, J = 8.3 Hz, 1H), 7.54 – 7.47 (3H), 7.31 (d, J = 7.5 Hz, 1H), 6.75 (d, J = 17.3 Hz, 1H), 6.50 (dd, J = 17.3, 10.4 Hz, 1H), 6.12 (d, J = 10.4 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 164.7, 146.6, 134.8, 133.1, 128.2, 127.9, 126.9, 126.6, 126.2, 125.6, 121.3, 118.2
HRMS (ESI+)	Calculated for C₁₃H₁₁O₂ [M+H]⁺: 199.0754; found: 199.0763

N-methoxy-N-methylacrylamide
Identifier	148
¹H NMR (400 MHz, CDCl₃)	δ 6.68 (dd, J = 17.1, 10.4 Hz, 1H), 6.36 (d, J = 17.1 Hz, 1H), 5.70 (d, J = 10.4 Hz, 1H), 3.66 (s, 3H), 3.21 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 166.5, 129.0, 125.9, 61.8, 32.3
HRMS (ESI+)	Calculated for C₅H₁₀NO₂ [M+H]⁺: 116.0706; found: 116.0762

diphenylmethanone O-acryloyl oxime
Identifier	149
¹H NMR (400 MHz, CDCl₃)	δ 7.61 (d, J = 7.7 Hz, 2H), 7.50 – 7.42 (m, 4H), 7.41 – 7.32 (m, 4H), 6.32 (d, J = 17.3 Hz, 1H), 6.08 (dd, J = 17.3, 10.6 Hz, 1H), 5.83 (d, J = 10.6 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 165.4, 163.7, 134.8, 132.7, 132.0, 131.1, 129.8, 129.2, 129.0, 128.5, 128.3, 126.7
HRMS (ESI+)	Calculated for C₁₆H₁₃NNaO₂ [M+Na]⁺: 274.0838; found: 274.0844

ethyl 3-(1-benzoylpiperidin-4-ylidene)acrylate
Identifier	161
¹H NMR (400 MHz, CDCl₃)	δ 7.42 (bs, 5H), 5.57 (s, 1H), 4.19 (q, J = 7.1 Hz, 2H), 3.87 (bs, 2H), 3.53 (bs, 2H), 2.37 (bs, 4H), 1.28 (t, J = 7.2 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 207.8, 170.7, 166.2, 135.9, 130.0, 128.7, 127.0, 102.8, 87.6, 61.0, 14.4
HRMS (ESI+)	Calculated for C₁₇H₂₀NO₃ [M+H]⁺: 286.1438; found 286.1515

ethyl 4-(4-isobutylphenyl)penta-2,3-dienoate
Identifier	162
¹H NMR (400 MHz, CDCl₃)	δ 7.30 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 5.88 (d, J = 3.0 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 2.47 (d, J = 7.1 Hz, 2H), 2.19 (d, J = 2.9 Hz, 3H), 1.87 (dq, J = 13.5, 6.7 Hz, 1H), 1.29 (t, J= 7.1 Hz, 3H), 0.90 (d, J = 6.6 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 214.2, 165.9, 141.7, 131.7, 129.5, 126.1, 105.4, 89.8, 61.0, 45.2, 30.3, 22.5, 16.3, 14.4
HRMS (ESI+)	Calculated for C₁₇H₂₃O₂ [M+H]⁺: 259.1693; found 259.1695

(E)-3-(3-hydroxyphenyl)-1-phenylprop-2-en-1-one
Identifier	86
¹H NMR (400 MHz, CDCl₃)	δ 7.91 (d, J = 7.3 Hz, 2H), 7.67 (d, J = 15.7 Hz, 1H), 7.49 (t, J = 7.3 Hz, 1H), 7.42 – 7.38 (m, 3H), 7.21 – 7.11 (m, 2H), 7.06 (s, 1H), 6.82 (d, J = 7.9 Hz, 1H), 5.62 (bs, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.8, 156.2, 144.8, 138.3, 136.6, 133.1, 130.4, 128.8, 128.7, 122.6, 121.4, 117.9, 115.0
HRMS (ESI+)	Calculated for C₁₅H₁₃O₂ [M+H]⁺: 225.0910; found 225.0944

2-phenylacrylic acid
Identifier	106
¹H NMR (400 MHz, CDCl₃)	δ 7.45 – 7.43 (m, 2H), 7.39 – 7.36 (m, 3H), 6.54 (s, 1H), 6.03 (s, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.8, 140.7, 136.3, 129.5, 128.6, 128.5, 128.3

(E)-1-(4-bromo-1H-pyrazol-1-yl)-3-phenylprop-2-en-1-one
Identifier	88
¹H NMR (400 MHz, CDCl₃)	δ 8.40 (s, 1H), 8.04 (d, J = 16.0 Hz, 1H), 7.83 d, J = 16.0 Hz, 1H), 7.72 (s, 1H), 7.70 – 7.68 (m, 2H), 7.45 – 7.43 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 162.8, 148.9, 144.4, 134.4, 131.5, 129.2, 129.1, 128.8, 114.6, 99.6
HRMS (ESI+)	Calculated for C₁₂H₁₀BrN₂O [M+H]⁺: 276.9971; found: 276.9986

methyl 2-(acetoxy(phenyl)methyl)acrylate
Identifier	94
¹H NMR (400 MHz, CDCl₃)	δ 7.39 – 7.28 (m, 5H), 6.69 (s, 1H), 6.40 (s, 1H), 5.86 (s, 1H), 3.71 (s, 3H), 2.10 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.5, 165.5, 139.8, 137.9, 128.6, 128.5, 127.8, 125.9, 73.2, 52.1, 21.2

benzyl 2-(hydroxy(phenyl)methyl)acrylate
Identifier	96
¹H NMR (400 MHz, CDCl₃)	δ 7.38 – 7.25 (m, 10H), 6.41 (s, 1H), 5.88 (s, 1H), 5.59 (s, 1H), 5.16 (s, 2H), 2.98 (s, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 166.2, 142.1, 141.4, 135.6, 128.7, 128.6, 128.4, 128.2, 128.0, 126.8, 126.5, 73.3, 66.8

benzyl 2-(hydroxy(4-(trifluoromethyl)phenyl)methyl)acrylate
Identifier	97
¹H NMR (400 MHz, CDCl₃)	δ 7.59 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.34 – 7.33 (m, 3H), 7.26 – 7.23 (m, 2H), 6.43 (s, 1H), 5.88 (s, 1H), 5.61 (d, J = 6.0 Hz, 1H), 5.16 (s, 1H), 3.14 (d, J = 6.0 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 165.9, 145.2, 141.4, 136.3, 130.00 (q, JC-F = 32.4 Hz), 128.6, 128.5, 128.2, 127.1, 126.9, 125.40 (q, JC-F = 3.7 Hz), 123.8 (q, JC-F = 210.0 Hz), 66.9, 66.4 142.1, 141.4, 135.6, 128.7, 128.6, 128.4, 128.2, 128.0, 126.8, 126.5, 73.3, 66.8
¹⁹F NMR (377 MHz, CDCl₃)	δ −62.5

(E)-6-bromo-1-phenylhex-2-en-1-one
Identifier	102
¹H NMR (400 MHz, CDCl₃)	δ 7.94 (d, J = 7.2 Hz, 2H), 7.59 – 7.54 (m, 1H), 7.47 (t, J = 7.2 Hz, 2H), 7.05 – 6.94 (m, 2H), 3.45 (t, J = 6.5 Hz, 2H), 2.51 (q, J = 6.8 Hz, 2H), 2.13 – 2.06 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 190.6, 147.2, 137.8, 132.9, 128.7, 128.6, 127.1, 32.8, 31.1, 31.0
HRMS (ESI+)	Calculated for C₁₂H₁₆BrO [M+H]⁺: 253.0223; found: 253.0255

(8S, 9S, 10R, 13R)-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 acrylate
Identifier	191
¹H NMR (400 MHz, CDCl₃)	δ 6.38 (dd, J = 17.3, 1.6 Hz, 1H), 6.10 (dd, J = 17.3, 10.4 Hz, 1H), 5.80 (dd, J = 10.4, 1.6 Hz, 1H), 5.39 (d, J = 5.0 Hz, 1H), 4.69 (m, 1H), 2.36 (d, J = 8.0 Hz, 2H), 2.03 – 1.78 (m, 5H), 1.68 – 1.08 (m, 18H), 1.03 – 0.95 (m, 6H), 0.92 – 0.90 (m, 3H), 0.86 (d, J = 6.5 Hz, 6H), 0.68 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 165.8, 139.8, 130.4, 129.2, 122.9, 74.3, 56.8, 56.3, 50.2, 42.5, 39.9, 39.7, 38.2, 37.1, 36.8, 36.3, 35.9, 32.1, 32.0, 28.4, 28.2, 27.9, 24.4, 24.0, 23.0, 22.7, 21.2, 19.5, 18.9, 12.0
HRMS (ESI+)	Calculated for C₃₀H₄₉O₂ [M+H]⁺: 441.3728; found: 441.3736

(2R,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl acrylate
Identifier	184
Sample qualifier	Mixture of α and β tetrahydropyran
¹H NMR (400 MHz, CDCl₃)	δ 7.35 – 7.23 (m, 18H), 7.17 – 7.11 (m, 2H), 6.64 – 6.34 (m, 2H), 6.22 – 6.07 (m, 1H), 5.92 (d, J = 10.5 Hz, 1H), 5.00 – 4.44 (m, 8H), 4.01 – 3.56 (m, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 164.62, 164.43, 138.77, 138.54, 138.16, 138.05, 137.96, 137.75, 132.60, 132.27, 128.64 – 128.48 (m, 15C)), 128.24, 128.19 – 128.07 (m, 10C), 128.05 – 127.94 (m, 10C), 127.93 – 127.75 (m, 4C), 94.47, 90.43, 84.95, 81.86, 81.06, 79.03, 77.37, 77.05, 75.87, 75.84 (2C), 75.72, 75.48, 75.17 (2C), 73.71, 73.67, 73.29, 73.05, 68.20
HRMS (ESI+)	Calculated for C₃₇H₄₀O₇ [M+H]⁺: 596.2769; found: 5955.2777

N-methyl-N-(3-phenyl-3-(4-(trifluoromethyl)phenoxy)propyl)propiolamide
Identifier	185
¹H NMR (400 MHz, CDCl₃)	δ 7.43 (d, J = 7.9 Hz, 2H), 7.38 – 7.28 (m, 5H), 6.93 – 6.84 (m, 2H), 5.21 (dd, J = 8.7, 3.8 Hz, 1H), 4.00 – 3.89 (m, 0.5H), 3.76 – 3.67 (m, 0.5H), 3.62 (t, J = 7.2 Hz, 1H), 3.20 (s, 1.3H), 3.12 (s, 0.3H) 2.98 (s, 1.7H), 2.84 (s, 0.7H), 2.32 – 2.07 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 160.3, 160.2, 153.7, 140.5, 140.1, 129.1 (d, JC-F = 11.7 Hz), 128.3, 128.2, 126.9 (q, JC-F = 3.7 Hz), 125.8, 125.7, 115.8 (d, JC-F = 6.2 Hz), 79.5, 75.9, 75.5, 47.9, 44.3, 37.4, 32.7
HRMS (ESI+)	Calculated for C₂₀H₁₉F₃NO₂ [M+H]⁺: 362.1363; found: 362.1372

2-((2-(6-methoxynaphthalen-2-yl)propanoyl)oxy)ethyl methacrylate
Identifier	183
¹H NMR (400 MHz, CDCl₃)	δ 7.70 – 7.66 (m, 3H),7.39 (dd, J = 8.5, 1H), 7.15 – 7.07 (m, 2H), 5.94 (s, 1H), 5.44 (s, 1H), 4.35 – 4.28 (m, 4H), 3.91 (s, 3H), 3.88 (q, J = 7.2, 1H), 1.82 (s, 3H), 1.58 (d, J = 7.2 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.5, 167.1, 157.8, 135.9, 135.5, 133.9, 129.4, 129.1, 127.3, 126.3, 126.1, 126.0, 119.1, 105.7, 62.5, 62.4, 55.4, 45.5, 18.5, 18.2
HRMS (ESI+)	Calculated for C₂₀H₂₃O₅ [M+H]⁺: 343.1540; found: 343.1547

1-(4-(2-chlorodibenzo[b,f][1,4]oxazepin-11-yl)piperazin-1-yl)prop-2-yn-1-one
Identifier	186
¹H NMR (400 MHz, CDCl₃)	δ 7.42 (dd, J = 8.6, 2.4 Hz, 1H), 7.32 (d, J = 2.3 Hz, 1H), 7.21 (d, J = 8.7 Hz, 1H), 7.18 – 7.14 (m, 1H), 7.14 – 7.08 (m, 2H), 7.03 (t, J = 7.5 Hz, 1H), 3.92 (bs, 2H), 3.77 (bs, 2H), 3.62 (bs, 2H), 3.53 (bs, 2H), 3.18 (s, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 159.6, 158.7, 152.2, 152.0, 139.5, 133.2, 130.7, 129.0, 127.2, 126.1, 125.4, 124.7, 123.1, 120.3, 80.1, 75.2, 46.7, 41.4
HRMS (ESI+)	Calculated for C₂₀H₁₇ClN₃O₂ [M+H]⁺: 366.1004; found: 366.1018

5′,5′-dimethylhexahydro-1H-spiro[pentalene-2,2′-[1,3]dioxan]-5-yl propiolate
Identifier	190
¹H NMR (400 MHz, CDCl₃)	δ 5.32 (bs, 1H), 3.44 (s, 4H), 2.84 (s, 1H), 2.69 (bs, 2H), 2.21 – 2.09 (m, 2H), 2.07 – 1.95 (m, 2H), 1.71 (t, J = 12.0 Hz, 4H), 0.94 (s, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 152.5, 110.1, 81.0, 75.2, 74.2, 74.2, 72.2, 72.1, 39.9, 39.1, 38.2, 30.2, 22.6, 22.6

(8S, 9S, 10R, 13R)-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 bicyclo[1.1.0]butane-1-carboxylate
Identifier	199
¹H NMR (400 MHz, CDCl₃)	δ 5.37 – 5.35 (m, 1H), 4.67 – 4.59 (m, 1H), 2.35 – 2.25 (m, 4H), 2.03 – 1.93 (m, 3H), 1.87 – 1.78 (m, 3H), 1.59 – 1.24 (m, 11H), 1.19 – 1.05 (m, 9H), 1.01 – 0.95 (m, 6H), 0.92 – 0.90 (m, 3H), 0.87 – 0.85 (m, 6H), 0.67 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.7, 139.8, 122.7, 74.2, 56.8, 56.3, 50.2, 42.4, 39.9, 39.6, 38.3, 37.1, 36.7, 36.3, 35.9, 35.6, 32.0, 31.9, 28.4, 28.1, 27.9, 25.9, 24.4, 24.0, 23.0, 22.7, 21.2, 19.5, 18.9, 16.5, 12.0, 9.4
HRMS (ESI+)	Calculated for C₃₂H₅₁O₂ [M+H]⁺: 467.3884; found: 467.3890

ethyl (6S)-6-((5R,8S,9R,10R,13S,14R,17S)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)hepta-2,3-dienoate
Identifier	163
¹H NMR (400 MHz, CDCl₃)	δ 5.62 – 5.49 (m, 2H), 4.24 – 4.11 (m, 2H), 2.96 – 2.78 (m, 3H), 2.38 – 1.91 (m, 14H), 1.90 – 1.79 (m, 1H), 1.69 – 1.54 (m, 1H), 1.48 – 1.41 (m, 1H), 1.39 (s, 3H), 1.31 – 1.23 (m, 5H), 1.08 (s, 3H), 0.93 (t, J = 6.5 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 212.6, 212.5, 211.7, 209.0, 208.7, 208.6, 166.3, 93.2, 93.0, 87.7, 87.6, 60.7, 60.7, 56.8, 51.7, 49.0, 46.8, 45.5, 45.5, 45.2, 44.9, 42.8, 38.6, 36.5, 36.3, 36.3, 36.0, 35.2, 34.1, 33.8, 27.7, 27.6, 25.1, 25.1, 21.9, 19.0, 14.2, 11.9
HRMS (ESI+)	Calculated for C₂₈H₃₉O₅ [M+H]⁺: 455.2792; found 455.2810

(S)-3-fluoro-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol
Identifier	193
¹H NMR (400 MHz, CDCl₃)	δ 7.40 – 7.29 (m, 6H), 6.86 (d, J = 8.4 Hz, 1H), 6.66 – 6.61 (m, 1H), 5.45 – 5.40 (m, 1H), 4.88 (dd, J = 10.3, 8.6 Hz, 1H), 4.33 (t, J = 8.5 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 165.6 (d, JC-F = 2.2 Hz), 162.0 (d, JC-F = 3.0 Hz), 161.70 (d, JC-F = 257.6 Hz), 141.3, 133.7 (d, JC-F = 12.1 Hz), 129.1, 128.2, 126.7, 113.1 (d, JC-F = 3.0 Hz), 106.3 (d, JC-F = 22.2 Hz), 100.4 (d, JC-F = 13.1 Hz), 74.7, 67.4
¹⁹F NMR (377 MHz, CDCl₃)	δ −108.7 – (−108.8) (m)
HRMS (ESI+)	Calculated for C₁₅H₁₃FNO₂ [M+H]⁺: 258.0925; found: 258.0931

(S)-3-fluoro-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenyl acrylate
Identifier	194
¹H NMR (400 MHz, CDCl₃)	δ 7.50 – 7.44 (m, 1H), 7.38 – 7.29 (m, 5H), 7.10 (t, J = 9.0 Hz, 1H), 7.05 (d, J = 8.2 Hz, 1H), 6.56 (d, J = 17.3 Hz, 1H), 6.26 (dd, J = 17.3, 10.4 Hz, 1H), 5.95 (d, J = 9.1 Hz, 1H), 5.41 – 5.37 (m, 1H), 4.76 – 4.71 (m, 1H), 4.22 (t, J = 8.3 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 163.9, 161.4 (d, JC-F = 255.6 Hz), 158.2 (d, JC-F = 2.0 Hz), 150.2 (d, JC-F = 5.5 Hz), 141.8, 133.1, 132.0 (d, JC-F = 10.1 Hz), 128.7, 127.6, 127.2, 126.8, 118.9 (d, JC-F = 4.0 Hz), 113.9 (d, JC-F = 22.2 Hz), 111.8 (d, JC-F = 16.1 Hz), 74.5, 70.2
¹⁹F NMR (377 MHz, CDCl₃)	δ −109.15 (dd, J = 9.4, 6.0 Hz)
HRMS (ESI+)	Calculated for C₁₈H₁₅FNO₃ [M+H]⁺: 312.1030; found: 312.1038

methyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	29
¹H NMR (400 MHz, CDCl₃)	δ 7.78 – 7.63 (m, 4H), 7.57 – 7.40 (m, 8H), 7.34 – 7.27 (m, 4H), 7.24 – 7.13 (m, 3H), 7.08 (t, J = 7.2 Hz, 1H), 4.12 (t, J = 11.6 Hz, 1H), 2.94 – 2.83 (m, 1H), 2.82 (s, 3H), 2.50 (t, J = 14.4 Hz, 1H), 1.78 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.6, 145.8, 144.5, 133.3 (d, JC-P = 99.9 Hz), 132.1 (d, JC-P = 2.0 Hz), 132.0 (d, JC-P = 2.0 Hz), 131.8 (d, JC-P = 98.3 Hz), 131.4 (d, JC-P = 9.6 Hz), 130.8 (d, JC-P = 9.4 Hz), 128.85 (d, JC-P = 11.7 Hz), 128.9, 128.5 (d, JC-P = 11.8 Hz), 128.0, 127.2, 126.9, 126.6, 126.3, 63.9 (d, JC-P = 11.9 Hz), 51.4, 46.6, 29.3 (d, JC-P = 69.9 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.0
HRMS (ESI+)	Calculated for C₂₉H₂₉NO₃P [M+H]⁺: 470.1880; found 470.1933

ethyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	30
¹H NMR (400 MHz, CDCl₃)	δ 7.78 – 7.73 (m, 2H), 7.70 – 7.66 (m, 2H), 7.55 – 7.43 (m, 8H), 7.34 – 7.29 (m, 4H), 7.22 – 7.14 (m, 3H), 7.09 – 7.05 (m, 1H), 4.15 (t, J = 11.6 Hz, 1H), 3.32 – 3.24 (m, 1H), 3.11 – 3.03 (m, 1H), 2.93 – 2.85 (m, 1H), 2.52 (t, J = 14.8 Hz, 1H), 2.32 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.1, 145.9, 144.8, 133.5 (d, JC-P = 90.0 Hz), 132.1 (d, JC-P = 2.6 Hz), 132.0 (d, JC-P = 2.7 Hz), 131.6 (d, JC-P = 97 Hz), 131.6 (d, JC-P = 9.5 Hz), 130.8 (d, JC-P = 9.3 Hz), 128. 9, 128.8 (d, JC-P =11.7 Hz), 128.5 (d, JC-P =11.9 Hz), 127.9, 127.1, 126.9, 126.6, 126.5, 63.8 (d, JC-P = 11.4 Hz), 60.4, 46.3, 29.2 (d, JC-P = 69.8 Hz), 13.2
³¹P NMR (162 MHz, CDCl₃)	δ 30.0
HRMS (ESI+)	Calculated for C₃₀H₃₁NO₃P [M+H]⁺: 484.2036; found 484.1991

tert-butyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	31
¹H NMR (400 MHz, CDCl₃)	δ 7.85 – 7.74 (m, 2H), 7.68 – 7.59 (m, 2H), 7.56 – 7.37 (m, 9H), 7.29 – 7.22 (m, 3H), 7.21 – 7.12 (m, 3H), 7.09 (t, J = 7.3 Hz, 1H), 4.12 (t, J = 11.8 Hz, 1H), 3.00 – 2.84 (m, 1H), 2.40 (t, J = 14.2 Hz, 1H), 2.20 (bs, 2H), 0.79 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.0, 145.7, 145.4, 133.9 (d, JC-P = 99.4 Hz), 132.3 (d, JC-P = 98.1 Hz), 132.0 (d, JC-P = 2.8 Hz), 131.9 (d, JC-P = 2.7 Hz), 131.5 (d, JC-P = 9.4 Hz), 130.9 (d, JC-P = 9.4 Hz), 128.8 (d, JC-P = 11.6 Hz), 128.7 (d, JC-P = 11.6 Hz), 128.8, 127.9, 126.9, 126.9, 126.6, 126.5, 81.3, 64.1 (d, JC-P = 12.2 Hz), 46.4, 29.2 (d, JC-P = 70.2 Hz), 27.2
³¹P NMR (162 MHz, CDCl₃)	δ 30.2
HRMS (ESI+)	Calculated for C₃₂H₃₅NO₃P [M+H]⁺: 512.2349; found 512.2421

naphthalen-1-yl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	32
¹H NMR (400 MHz, CDCl₃)	δ 7.80 – 7.74 (m, 4H), 7.70 (d, J = 8.3 Hz, 1H), 7.64 – 7.52 (m, 5H), 7.51 – 7.38 (m, 3H), 7.35 – 7.12 (m, 12H), 6.81 (d, J = 7.5 Hz, 1H), 6.66 (d, J = 8.5 Hz, 1H), 4.47 (t, J = 11.5 Hz, 1H), 3.14 – 3.04 (m, 1H), 2.51 (dd, J = 14.9, 9.4 Hz, 1H), 2.30 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.3, 146.9, 145.6, 145.0, 134.3, 132.7 (d, JC-P = 99.6 Hz), 132.4 (d, JC-P = 99.0 Hz), 132.3 (d, JC-P = 3.6 Hz), 132.3 (d, JC-P = 3.6 Hz), 131.6 (d, JC-P = 9.4 Hz), 131.09 (d, JC-P = 9.4 Hz), 130.2, 128.8 (d, JC-P = 11.6 Hz), 128.9, 128.7 (d, JC-P = 11.6 Hz), 128.7, 127.5, 127.2, 127.1, 126.8, 126.3, 126.2, 126.1, 125.9, 125.5, 121.9, 118.3, 64.0 (d, JC-P = 12.3 Hz), 46.8 (d, JC-P = 2.1 Hz), 30.4 (d, JC-P = 70.1 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.8
HRMS (ESI+)	Calculated for C₃₈H₃₃NO₃P [M+H]⁺: 582.2193; found 582.2227

benzyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	33
¹H NMR (400 MHz, CDCl₃)	δ 7.78 – 7.73 (m, 2H), 7.69 – 7.64 (m, 3H), 7.52 – 7.41 (m, 8H), 7.33 – 7.28 (m, 4H), 7.21 – 7.17 (m, 4H), 7.13 – 7.09 (m, 2H), 7.06 – 7.03 (m, 1H), 6.73 (d, J = 6.2 Hz, 1H), 4.30 (d, J = 12.2 Hz, 1H), 4.19 (t, J = 11.6 Hz, 1H), 4.03 (d, J = 12.2 Hz, 1H), 2.96 (m, 1H), 2.56 (t, J = 14.8 Hz, 1H), 1.94 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.1, 135.0, 133.4 (d, JC-P = 99.0 Hz), 131.8 (d, JC-P= 97.0 Hz), 132.1 (d, JC-P = 2.8 Hz), 132.0 (d, JC-P = 3.0 Hz), 131.5 (d, JC-P = 9.4 Hz), 130.8 (d, JC-P = 9.3 Hz), 128.9 (d, JC-P = 11.7 Hz), 128.9, 128.6 (d, JC-P = 11.8 Hz), 128.3, 128.2, 128.1, 128.0, 127.1, 126.9, 126.7, 126.4, 66.7, 46.6, 31.1, 29.5 (d, JC-P = 70.1 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.9
HRMS (ESI+)	Calculated for C₃₅H₃₃NO₃P [M+H]⁺: 546.2193; found 546.2224

2,2,2-trifluoroethyl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	34
¹H NMR (400 MHz, CDCl₃)	δ 7.74 – 7.65 (m, 4H), 7.58 – 7.51 (m, 1H), 7.51 – 7.42 (m, 6H), 7.33 – 7.28 (m, 5H), 7.23 – 7.17 (m, 3H), 7.11 – 7.07.08 (m, 1H), 4.16 (t, J = 11.4 Hz, 1H), 3.75 – 3.69 (m, 1H), 3.52 – 3.46 (m, 1H), 2.89 – 2.84 (m, 1H), 2.50 (t, J = 13.9 Hz, 1H), 2.25 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.6, 145.1, 144.3, 132.5 (d, JC-P = 99.8 Hz), 132.2 (d, JC-P = 2.6 Hz), 131.7 (d, JC-P = 101.7 Hz), 132.0 (d, JC-P = 2.9 Hz), 131.2 (d, JC-P = 9.5 Hz), 130.8 (d, JC-P = 9.4 Hz), 128.8 (d, JC-P = 13.2 Hz), 128.8, 128.6 (d, JC-P = 11.7 Hz), 128.1, 127.2, 126.9, 126.5, 125.9, 122.4 (d, JC-F = 277.0 Hz), 63.8 (d, JC-P = 11.9 Hz), 61.0 (q, JC-F = 36.8 Hz), 46.6, 29.5 (d, JC-P = 69.6 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.6
¹⁹F NMR (377 MHz, CDCl₃)	δ −73.4
HRMS (ESI+)	Calculated for C₃₀H₂₈F₃NO₃P [M+H]⁺: 538.1753; found 538.1829

2-((diphenylphosphoryl)methyl)-3-hydroxy-N-methoxy-N-methyl-3,3-diphenylpropanamide
Identifier	35
NMR reporting qualifier	The compound was observed as a mixture of rotamers in CDCl₃ at 298 K. Where distinguishable, signals corresponding to the major and minor rotamers are reported separately. All the signal were assigned for the major one. Some ¹³C for the minor rotamer are not visible
¹H NMR (400 MHz, CDCl₃)	δ 7.82 – 7.73 (m, 2H, major and minor rotamer), 7.69 – 7.60 (m, 3H, major and minor rotamer), 7.53 (d, J = 7.9 Hz, 2H, major and minor rotamer), 7.52 – 7.38 (m, 6H, major and minor rotamer), 7.40 – 7.25 (m, 2H, major and minor rotamer), 7.28 – 7.02 (m, 5H, major and minor rotamer), 4.65 (t, J = 11.5 Hz, 1H, major rotamer), 4.22 (t, J = 11.5 Hz, 0.30H, minor rotamer), 3.23 (s, 3H, major rotamer), 3.23 – 3.04 (m, 1.30H, major and minor rotamer), 2.78 (s, 1H, minor rotamer), 2.71 (s, 1H, minor rotamer), 2.59 – 2.45 (m, 1.30H, major and minor rotamer), 2.43 (s, 3H, major rotamer), 2.30 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.7 (major rotamer), 169.0 (minor rotamer), 146.6 (major rotamer), 146.4 (minor rotamer), 145.3 (minor rotamer), 145.2 (major rotamer), 134.2 (d, JC-P =99.1 Hz, major rotamer), 132.2 (d, JC-P = 97 Hz, major rotamer), 132.3 (d, JC-P =2.6 Hz, minor rotamer), 131.9 (d, JC-P =2.6 Hz, minor rotamer), 131.8 (d, JC-P = 2.8 Hz, major), 131.8 (d, JC-P = 2.8 Hz, major), 131.5 (d, JC-P = 9.5 Hz, major), 130.7 (d, JC-P = 9.5 Hz, major), 131.2 (d, JC-P = 9.7 Hz, minor),130.4 (d, JC-P = 9.7 Hz, minor), 128.9 (d, JC-P = 12.1 Hz, minor), 128.8 (d, JC-P = 11.6 Hz, minor),128.8 (d, JC-P = 11.7 Hz, major), 128.4 (d, JC-P = 11.7 Hz, major), 128.7 (major), 128.0 (minor), 127.5 (major), 127.4 (major), 127.2 (major), 127.1 (major), 127.0 (major), 126.7(minor), 126.5(minor), 126 4(minor), 64.6 (d, JC-P = 11.8 Hz, minor), 64.4 (d, JC-P = 12.3 Hz, major), 60.7 (major), 59.5 (minor), 41.4 (d, JC-P = 2.2 Hz, minor), 40.0 (d, JC-P = 2.2 Hz, major), 36.0 (major), 31.1 (minor), 29.9 (d, JC-P = 70.1 Hz, major), 29.6 (d, JC-P = 69.3 Hz, minor)
³¹P NMR (162 MHz, CDCl₃)	δ 30.38, 30.24
HRMS (ESI+)	Calculated for C₃₀H₃₂N₂O₃P [M+H]⁺: 499.2145; found 499.2200

3-amino-2-((diphenylphosphoryl)methyl)-N,N-dimethyl-3,3-diphenylpropanamide
Identifier	36
¹H NMR (400 MHz, CDCl₃)	δ 7.83 – 7.78 (m, 2H), 7.69 – 7.63 (m, 4H), 7.48 – 7.36 (m, 8H), 7.25 – 7.23 (m, 1H), 7.18 – 7.11 (m, 4H), 7.08 – 7.04 (m, 1H), 4.45 (t, J = 11.4 Hz, 1H), 3.12 (ddd, J = 15.6, 11.4, 5.1 Hz, 1H), 2.58 (t, J = 15.6 Hz, 1H), 2.50 (bs, 2H), 2.29 (s, 3H), 1.97 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.5, 146.9, 145.3, 134.4 (d, JC-P = 99.7 Hz), 131.9 (m), 131.5 (d, JC-P = 96.7 Hz), 131.4 (d, JC-P = 9 Hz), 130.4 (d, JC-P = 9.6 Hz), 128.8, 128.8 (d, JC-P = 11.6 Hz), 128.3 (d, JC-P = 11.8 Hz), 127.6, 127.5, 127.1, 126.5, 64.3 (d, JC-P = 12.3 Hz), 40.2 (d, JC-P = 1.9 Hz), 37.5, 35.0, 29.8 (d, JC-P = 69.6 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.5
HRMS (ESI+)	Calculated for C₃₀H₃₂N₂O₂P [M+H]⁺: 482.2196; found 482.2200

4-amino-3-((diphenylphosphoryl)methyl)-4,4-diphenylbutan-2-one
Identifier	37
¹H NMR (400 MHz, CDCl₃)	δ 7.82 – 7.69 (m, 4H), 7.59 – 7.42 (m, 12H), 7.23 – 7.11 (m, 4H), 4.28 (t, J = 11.7 Hz, 1H), 3.05 – 2.96 (m, 1H), 2.57 – 2.46 (m, 1H), 2.02 (bs, 2H), 1.18 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 212.8, 145.8, 145.0, 133.3 (d, JC-P = 99.0 Hz), 131.4 (d, JC-P = 106.6 Hz), 132.2 (d, JC-P = 2.7 Hz), 132.2 (d, JC-P = 2.7 Hz), 131.4 (d, JC-P = 9.5 Hz), 131.0 (d, JC-P = 9.4 Hz), 128.7 (d, JC-P = 11.8 Hz), 128.4, 127.2, 127.0, 126.8, 126.5, 63.7 (d, JC-P = 12.4 Hz), 51.5, 32.9, 30.4 (d, JC-P = 69.9 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.4
HRMS (ESI+)	Calculated for C₂₉H₂₉NO₂P [M+H]⁺: 454.1858; found 454.1973

3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanenitrile
Identifier	38
¹H NMR (400 MHz, CDCl₃)	δ 7.80 – 7.75 (m, 2H), 7.60 – 7.48 (m, 8H), 7.45 – 7.37 (m, 4H), 7.34 – 7.28 (m, 4H), 7.25 – 7.22 (m, 2H), 4.20 (t, J = 11.6 Hz, 1H), 2.64 – 2.47 (m, 2H), 2.04 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 144.4, 144.1, 132.74 (d, JC-P = 101.6Hz), 132.6 (d, JC-P = 2.7 Hz), 132.3 (d, JC-P = 2.83 Hz), 131.4 (d, JC-P = 9.6 Hz), 131.0 (d, JC-P = 103.7 Hz), 130.7 (d, JC-P = 9.58 Hz), 129.0 (d, JC-P =12.0 Hz), 127.0, 128.9 (d, JC-P = 12.1 Hz), 128.7, 127.7, 127.7, 126.8, 126.7, 119.7, 64.0 (d, JC-P =9.4 Hz), 35.8 (d, JC-P = 3.6 Hz), 29.1 (d, JC-P =69.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.5
HRMS (ESI+)	Calculated for C₂₈H₂₆N₂OP [M+H]⁺: 437.1705; found: 437.1667

(3-amino-2-((((diphenylmethylene)amino)oxy)carbonyl)-3,3-diphenylpropyl) diphenylphosphine oxide
Identifier	39
¹H NMR (400 MHz, CDCl₃)	δ 7.72 – 7.66 (m, 2H), 7.63 – 7.55 (m, 2H), 7.54 – 7.46 (m, 2H), 7.45 – 7.26 (m, 15H), 7.27 – 7.15 (m, 4H), 7.15 – 7.01 (m, 3H), 6.88 (d, J = 7.5 Hz, 2H), 3.91 (t, J = 11.8 Hz, 1H), 2.97 (dt, J = 15.3, 10.0 Hz, 1H), 2.48 (t, J = 14.6 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.6, 163.4, 145.6, 144.6, 134.9, 133.1 (d, JC-P = 99.6 Hz), 131.5 (d, JC-P = 9.5 Hz), 130.9 (d, JC-P = 9.5 Hz), 130.7, 130.2, 129.7, 129.3, 129.2, 128.8, 128.7 (d, JC-P = 6.9 Hz), 128.6, 128.3, 128.2, 128.0, 127.1, 126.9, 126.6, 126.4, 64.1 (d, JC-P = 11.6 Hz), 45.7, 30.0 (d, JC-P = 69.5 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.0
HRMS (ESI+)	Calculated for C₄₁H₃₆N₂O₃P [M+H]⁺: 635.2458; found 635.2551

3-amino-2-((diphenylphosphoryl)methyl)-3,3-bis(4-methoxyphenyl)propanenitrile
Identifier	40
¹H NMR (400 MHz, CDCl₃)	δ 7.78 (dd, J = 11.4, 7.7 Hz, 2H), 7.63 – 7.36 (m, 10H), 7.29 (d, J = 8.7 Hz, 2H), 6.83 (dd, J = 8.4, 4.9 Hz, 4H), 4.11 (t, J = 11.5 Hz, 1H), 3.78 (s, 6H), 2.63 (t, J = 14.9 Hz, 1H), 2.53 – 2.43 (m, 1H), 1.74 (s, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 158.8, 158.8, 136.7, 136.4, 132.8 (d, JC-P = 101.0 Hz), 132.5, 132.3, 131.4 (d, JC-P = 9.8 Hz), 130.7 (d, JC-P = 9.5 Hz), 130.9 (d, JC-P = 97.8 Hz), 129.0 (d, JC-P = 12.0 Hz), 128.9 (d, JC-P = 12.0 Hz), 128.0, 127.9, 119.8, 114.1, 113.8, 63.2 (d, JC-P = 9.4 Hz), 55.4, 36.1, 29.1 (d, JC-P = 69.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.6
HRMS (ESI+)	Calculated for C₃₀H₃₀N₂O₃P [M+H]⁺: 497.1989; found 497.1995

3-amino-3,3-bis(4-chlorophenyl)-2-((diphenylphosphoryl)methyl)propanenitrile
Identifier	41
¹H NMR (400 MHz, CDCl₃)	δ 7.79 (dd, J = 11.9, 6.7 Hz, 2H), 7.65 – 7.39 (m, 10H), 7.36 – 7.23 (m, 6H), 4.19 (t, J = 11.7 Hz, 1H), 2.60 – 2.41 (m, 2H), 1.72 (s, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 142.3, 142.2, 134.0, 133.9, 132.8 (d, JC-P = 2.5 Hz), 132.5 (d, JC-P = 1.9 Hz), 132.4 (d, JC-P = 102.5 Hz), 131.4 (d, JC-P = 9.8 Hz), 130.7 (d, JC-P = 9.4 Hz), 130.5 (d, JC-P = 101.0 Hz), 129.2 (d, JC-P = 13.4 Hz), 129.1 (d, JC-P = 11.9 Hz), 128.9, 128.2, 128.1, 119.3, 63.5 (d, JC-P = 9.1 Hz), 35.7 (d, JC-P = 2.5 Hz), 29.0 (d, JC-P = 69.0 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.4
HRMS (ESI+)	Calculated for C₂₈H₂₄Cl₂N₂OP [M+H]⁺: 505.0998; found 505.1041

3-amino-2-((bis(3,5-dimethylphenyl)phosphoryl)methyl)-3,3-diphenylpropanenitrile
Identifier	42
¹H NMR (400 MHz, CDCl₃)	δ 7.53 – 7.51 (m, 2H), 7.47 – 7.14 (m, 14H), 4.21 – 4.14 (m, 1H), 2.60 – 2.51 (m, 2H), 2.36 (s, 6H), 2.32 (s, 6H), 1.96 (br, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 144.5, 144.1, 138.7 (d, JC-P = 12.6 Hz), 138.6 (d, JC-P = 12.7 Hz), 134.2 (d, JC-P = 2.8 Hz), 134.0 (d, JC-P = 2.8 Hz), 132.4 (d, JC-P = 103.0 Hz), 130.9 (d, JC-P = 99.0 Hz), 129.0, 128.9, 128.6, 128.3 (d, JC-P = 9.5 Hz), 127.6 (d, JC-P = 8.3 Hz), 126.7, 119.9, 64.0 (d, JC-P = 9.3 Hz), 36.0 (d, JC-P = 3.0 Hz), 29.0 (d, JC-P = 68.9 Hz), 21.5 (4C)
³¹P NMR (162 MHz, CDCl₃)	δ 30.0
HRMS (ESI+)	Calculated for C₃₂H₃₄N₂OP [M+H]⁺: 493.2403; found 493.2464

tert-butyl 3-amino-2-((dicyclohexylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	43
¹H NMR (400 MHz, CDCl₃)	δ 7.69 (d, J = 7.4 Hz, 1H), 7.62 (d, J = 7.7 Hz, 1H), 7.34 – 7.27 (m, 3H), 7.25 – 7.15 (3H), 4.18 (t, J = 10.8 Hz, 1H), 2.21 – 1.62 (m, 26H), 1.09 (s, 9H)
¹³C NMR (101 MHz, CDCl₃)	δ 174.0, 128.8, 128.2 127.4, 126.9, 82.3, 46.89, 37.2 (d, JC-P = 64.0 Hz), 36.9 (d, JC-P = 64.2 Hz), 27.6, 27.0, 26.8 – 26.4 (m), 26.0 (d, JC-P = 12.3 Hz), 25.6 – 25.4 (m), 22.5 (d, JC-P = 90.9 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 50.6
HRMS (ESI+)	Calculated for C₃₂H₄₇NO₃P [M+H]⁺: 524.3288; found 524.3373

diethyl (3-amino-2-cyano-3,3-diphenylpropyl)phosphonate
Identifier	44
¹H NMR (400 MHz, CDCl₃)	δ 7.51 (d, J = 7.5 Hz, 2H), 7.42 – 7.27 (m, 8H), 4.18 – 4.06 (m, 4H), 4.03 – 3.93 (m, 1H), 2.07 – 1.97 (m, 2H), 1.60 (bs, 2H), 1.34 (dt, J = 9.7, 7.1 Hz, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 144.5, 143.8, 129.0, 128.7, 127.8, 127.7, 126.6, 126.5, 120.0, 63.7 (d, JC-P = 13.4 Hz), 62.6 (d, JC-P = 6.6 Hz), 62.5 (d, JC-P = 6.2 Hz), 37.6 (d, JC-P = 4.7 Hz), 25.3 (d, JC-P = 143.9 Hz), 16.5 (d, JC-P = 6.2 Hz), 16.4 (d, JC-P = 6.2 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 27.0
HRMS (ESI+)	Calculated for C₂₀H₂₆N₂O₃P [M+H]⁺: 373.1676; found 373.1678

methyl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)acrylate
Identifier	45
¹H NMR (400 MHz, CDCl₃)	δ 7.62 (dd, J = 12.0, 7.3 Hz, 4H), 7.53 – 7.46 (m, 2H), 7.46 – 7.37 (m, 8H), 7.22 – 7.12 (m, 6H), 6.86 (d, J = 19.4 Hz, 1H), 3.35 (s, 3H), 3.07 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.9 (d, JC-P = 20.5 Hz), 163.0, 146.3, 134.0 (d, JC-P = 108.8 Hz), 131.7 (d, JC-P = 2.7 Hz), 131.0 (d, JC-P = 9.7 Hz), 128.7 (d, JC-P = 12.3 Hz), 127.9 (d, JC-P = 95.2 Hz), 127.9, 127.8, 127.0, 66.6 (d, JC-P = 4.7 Hz), 52.2
³¹P NMR (162 MHz, CDCl₃)	δ 19.6
HRMS (ESI+)	Calculated for C₂₉H₂₇NO₃P [M+H]⁺: 468.1723; found 468.1751

benzyl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)acrylate
Identifier	46
¹H NMR (400 MHz, CDCl₃)	δ 7.61 (dd, J = 12.0, 7.7 Hz, 4H), 7.52 – 7.46 (m, 2H), 7.45 – 7.35 (m, 8H), 7.29 – 7.22 (m, 3H), 7.16 – 7.10 (m, 6H), 7.03 – 6.98 (m, 2H), 6.93 (d, J = 19.3 Hz, 1H), 4.77 (s, 2H), 3.47 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.2 (d, JC-P = 20.7 Hz), 162.5, 145.9, 135.0, 133.9 (d, JC-P = 108.6 Hz), 131.8 (d, JC-P = 2.9 Hz), 131.0 (d, JC-P = 9.8 Hz), 129.7, 128.7 (d, JC-P = 12.4 Hz), 128.5, 128.5 (d, JC-P = 88.6 Hz), 128.4, 128.0, 127.9, 127.1, 67.4, 66.7 (d, JC-P = 4.7 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 19.8
HRMS (ESI+)	Calculated for C₃₅H₃₁NO₃P [M+H]⁺: 544.2036; found 544.2097

(E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)-N-methoxy-N-methylacrylamide
Identifier	47
¹H NMR (400 MHz, CDCl₃)	δ 7.60 – 7.44 (m, 10H), 7.43 – 7.35 (m, 4H), 7.18 – 7.01 (m, 6H), 6.30 (d, J = 19.9 Hz, 1H), 3.47 (s, 2.4H), 3.39 – 2.94 (m, 3.2H), 2.63 (s, 2.4H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.9 (d, JC-P = 19.5 Hz), 168.7, 145.9, 133.3 (d, JC-P = 108.3 Hz), 131.8, 130.9 (d, JC-P = 9.4 Hz), 128.7 (d, JC-P = 12.2 Hz), 128.0, 127.5, 126.8, 120.5 (d, JC-P = 94.7 Hz), 66.0, 60.9, 32.2
³¹P NMR (162 MHz, CDCl₃)	δ 18.4
HRMS (ESI+)	Calculated for C₃₀H₃₀N₂O₃P [M+H]⁺: 497.1989; found 497.2059

(E)-2-(aminodiphenylmethyl)-N,N-dibenzyl-3-(diphenylphosphoryl)acrylamide
Identifier	48
¹H NMR (400 MHz, CDCl₃)	δ 7.61 (bs, 2H), 7.52 – 7.22 (m, 15H), 7.20 – 7.03 (m, 12H), 6.49 – 6.38 (m, 3H), 5.37 (d, J = 16.4 Hz, 1H), 5.13 (d, J = 13.9 Hz, 1H), 3.84 (d, J = 16.9 Hz, 1H), 3.57 (d, J = 14.1 Hz, 1H), 2.94 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.1 (d, JC-P = 19.0 Hz), 164.8, 148.2, 145.1, 136.0, 135.4, 134.0 (d, JC-P = 107.9 Hz), 131.8 – 130.4 (m), 129.1 (d, JC-P = 5.3 Hz), 128.8 – 128.5 (m), 128.5, 128.4 – 128.1 (m), 128.0, 127.7, 127.3, 127.0, 126.7, 121.2 (d, JC-P = 93.4 Hz), 66.6 (d, JC-P = 5.3 Hz), 50.2, 46.4
³¹P NMR (162 MHz, CDCl₃)	δ 18.9
HRMS (ESI+)	Calculated for C₄₂H₃₈N₂O₂P [M+H]⁺: 633.2665; found 633.2740

(E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)-1-phenylprop-2-en-1-one
Identifier	49
¹H NMR (400 MHz, CDCl₃)	δ 7.87 (d, J = 7.9 Hz, 2H), 7.57 – 7.45 (m, 7H), 7.44 – 7.34 (m, 10H), 7.12 – 7.02 (m, 6H), 6.29 (d, J = 19.5 Hz, 1H), 3.29 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 196.7 (d, JC-P = 17.8 Hz), 168.2 (d, JC-P = 2.9 Hz), 146.3, 136.0, 133.5, 133.1 (d, JC-P = 108.3 Hz), 131.9 (d, JC-P = 2.9 Hz), 131.0 (d, JC-P = 9.8 Hz), 130.2, 128.7 (d, JC-P = 12.4 Hz), 128.4, 128.4, 127.8, 127.0, 124.4 (d, JC-P = 92.6 Hz), 67.2 (d, JC-P = 5.4 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 19.6
HRMS (ESI+)	Calculated for C₃₅H₃₁NO₃P [M+H]⁺: 514.1930; found 514.1961

(E)-3-(aminodiphenylmethyl)-4-(diphenylphosphoryl)but-3-en-2-one
Identifier	50
¹H NMR (400 MHz, CDCl₃)	δ 7.60 (dd, J = 12.1, 7.1 Hz, 4H), 7.54 – 7.47 (m, 2H), 7.46 – 7.33 (m, 8H), 7.22 – 7.11 (m, 6H), 6.43 (d, J = 19.0 Hz, 1H), 3.60 (s, 2H), 1.95 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 203.3 (d, JC-P = 17.1 Hz), 171.3, 145.7, 133.6 (d, JC-P = 108.6 Hz), 131.9 (d, JC-P = 2.9 Hz), 131.0 (d, JC-P = 9.8 Hz), 129.8 (d, JC-P = 12.4 Hz), 128.1, 127.3, 123.6 (d, JC-P = 94.8 Hz), 66.7 (d, JC-P = 5.4 Hz), 30.2
³¹P NMR (162 MHz, CDCl₃)	δ 20.1
HRMS (ESI+)	Calculated for C₂₉H₂₇NO₂P [M+H]⁺: 452.1774; found 452.1800

methyl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)-3-phenylacrylate
Identifier	51
¹H NMR (400 MHz, CDCl₃)	δ 7.57 (d, J = 7.5 Hz, 4H), 7.50 – 7.39 (m, 6H), 7.35 – 7.17 (m, 10H), 7.06 – 6.99 (m, 1H), 6.97 – 6.90 (m, 2H), 6.75 (d, J = 7.7 Hz, 2H), 3.92 (bs, 2H), 2.68 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.2 (d, JC-P = 20.3 Hz), 162.0 (d, JC-P = 4.5 Hz), 147.5, 137.1 (d, JC-P = 10.9 Hz), 135.2 (d, JC-P = 85.7 Hz), 132.7 (d, JC-P = 9.4 Hz), 131.7 (d, JC-P = 2.9 Hz), 131.4 (d, JC-P = 107.5 Hz), 131.3 (d, JC-P = 3.6 Hz), 128.5, 128.0 (d, JC-P = 12.4 Hz), 127.6, 127.5 (d, JC-P = 1.9 Hz), 127.3, 127.1, 66.8 (d, JC-P = 4.4 Hz), 50.8
³¹P NMR (162 MHz, CDCl₃)	δ 27.4
HRMS (ESI+)	Calculated for C₃₅H₃₁NO₃P [M+H]⁺: 544.2037; found 544.2097

methyl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)but-2-enoate
Identifier	52
¹H NMR (400 MHz, CDCl₃)	δ 7.55 – 7.35 (m, 14H), 7.22 – 7.11 (m, 6H), 4.04 (bs, 2H), 3.19 (s, 3H), 1.74 (d, J = 13.4 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.2 (d, JC-P = 21.4 Hz), 161.9, 147.0, 132.0 (d, JC-P = 9.4 Hz), 131.0, 128.8 (d, JC-P = 66.5 Hz), 128.6 (d, JC-P = 12.0 Hz), 128.3, 127.5, 127.0 (d, JC-P = 87.9 Hz), 126.9, 66.4 (d, JC-P = 5.1 Hz), 51.4, 21.7 (d, JC-P = 13.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.3
HRMS (ESI+)	Calculated for C₃₀H₂₉NO₃P [M+H]⁺: 482.1880; found 482.1940

methyl (E)-2-(aminobis(4-methoxyphenyl)methyl)-3-(diphenylphosphoryl)acrylate
Identifier	53
¹H NMR (400 MHz, CDCl₃)	δ 7.62 (dd, J = 12.0, 7.2 Hz, 4H), 7.52 – 7.46 (m, 2H), 7.46 – 7.38 (m, 4H), 7.29 (d, J = 8.9 Hz, 4H), 6.78 (d, J = 19.6 Hz, 1H), 6.70 (d, J = 8.9 Hz, 4H), 3.75 (s, 6H), 3.39 (s, 3H), 2.76 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.0 (d, JC-P = 20.7 Hz), 163.6, 158.4, 138.7, 134.1 (d, JC-P = 108.6 Hz), 131.7 (d, JC-P = 2.9 Hz), 130.9 (d, JC-P = 9.8 Hz), 129.0, 128.7 (d, JC-P = 12.4 Hz), 127.1 (d, JC-P = 95.9 Hz), 113.1, 65.7 (d, JC-P = 4.7 Hz), 55.3, 52.3
³¹P NMR (162 MHz, CDCl₃)	δ 19.5
HRMS (ESI+)	Calculated for C₃₀H₂₉NO₃P [M+H]⁺: 528.1935; found 528.1941

methyl (E)-2-(aminobis(4-chlorophenyl)methyl)-3-(diphenylphosphoryl)acrylate
Identifier	54
¹H NMR (400 MHz, CDCl₃)	δ 7.61 – 7.49 (m, 6H), 7.47 – 7.40 (m, 4H), 7.32 (d, J = 8.7 Hz, 4H), 7.08 (d, J = 8.7 Hz, 4H), 6.84 (d, J = 19.0 Hz, 1H), 3.42 (s, 3H), 3.32 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.8 (d, JC-P = 20.3 Hz), 162.8, 144.7, 133.2 (d, JC-P = 108.6 Hz), 133.0, 132.0 (d, JC-P = 2.9 Hz), 130.8 (d, JC-P = 9.8 Hz), 128.9, 128.8 (d, JC-P = 12.7 Hz), 128.2 (d, JC-P = 93.4 Hz), 128.1, 65.5 (d, JC-P = 4.7 Hz), 52.5
³¹P NMR (162 MHz, CDCl₃)	δ 19.2
HRMS (ESI+)	Calculated for C₂₉H₂₅Cl₂NO₃P [M+H]⁺: 536.0944; found 536.0742

methyl (Z)-3-amino-2-((diphenylphosphoryl)methyl)-3-phenylacrylate
Identifier	58 and 58’
¹H NMR (400 MHz, CDCl₃), major diastereisomer	δ 7.82 (dd, J = 10.7, 7.4 Hz, 4H), 7.58 – 7.41 (m, 6H), 7.39 – 7.29 (m, 5H), 6.01 (bs, 2H), 3.70 (d, J = 12.2 Hz, 2H), 3.08 (s, 3H)
¹³C NMR (101 MHz, CDCl₃), major diastereisomer	δ 169.1 (d, JC-P = 2.5 Hz), 160.4 (d, JC-P = 3.6 Hz), 140.0, 133.3 (d, JC-P = 101.7 Hz), 131.2 (d, JC-P = 6.2 Hz), 131.1, 129.1, 128.6 (d, JC-P = 11.6 Hz), 128.1, 128.0 (d, JC-P = 1.7 Hz), 89.9 (d, JC-P = 7.6 Hz), 50.5, 32.1 (d, JC-P = 70.5 Hz)
³¹P NMR (162 MHz, CDCl₃), major diastereisomer	δ 37.0
¹H NMR (400 MHz, CDCl₃), minor diastereisomer	δ 7.54 (dd, J = 10.5, 7.7 Hz, 4H), 7.48 – 7.41 (m, 2H), 7.40 – 7.28 (m, 9H), 3.27 (d, J = 11.5 Hz, 2H), 3.21 (s, 3H), 1.71 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃), minor diastereisomer	δ 170.2, 161.6 (d, JC-P = 5.4 Hz), 137.8 (d, JC-P = 1.2 Hz), 134.1 (d, JC-P = 95.6 Hz), 131.3 (d, JC-P = 8.9 Hz), 131.2 (d, JC-P = 3.0 Hz), 129.2, 128.8, 128.3, 128.3 (d, JC-P = 11.3 Hz), 85.5 (d, JC-P = 7.9 Hz), 50.3, 30.7 (d, JC-P = 71.0 Hz)
³¹P NMR (162 MHz, CDCl₃), minor diastereisomer	δ 28.8
HRMS (ESI)	Calculated for C₂₃H₂₃NO₃P [M+H]⁺: 392.1411; found: 392.1398

benzyl (1r,3r)-1-(aminodiphenylmethyl)-3-(diphenylphosphoryl)cyclobutane-1-carboxylate
Identifier	69
¹H NMR (400 MHz, CDCl₃)	δ 7.54 – 7.45 (m, 7H), 7.40 – 7.35 (m, 4H), 7.25 – 7.19 (m, 12H), 7.00 (d, J = 7.0 Hz, 2H), 4.95 (s, 2H), 3.20 (p, J = 9.4 Hz, 1H), 2.93 – 2.83 (m, 2H), 2.58 – 2.52 (m, 2H), 2.29 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 176.0, 146.1, 135.4, 132.4 (d, JC-P = 98.0 Hz), 131.8 (d, JC-P = 2.0 Hz), 131.1 (d, JC-P = 9.1 Hz), 128.7 (d, JC-P = 11.4 Hz), 128.6, 128.4, 128.3, 128.0, 127.9, 127.1, 67.3, 65.6 (d, JC-P = 2.0 Hz), 56.9 (d, JC-P = 19.2 Hz), 29.6 (d, JC-P = 4.0 Hz), 28.5 (d, JC-P = 70.7 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.7
HRMS (ESI+)	Calculated for C₃₇H₃₅NO₃P [M+H]⁺: 572.2349; found 572.2398

(3-(aminodiphenylmethyl)-3-(phenylsulfonyl)cyclobutyl)diphenylphosphine oxide
Identifier	70
¹H NMR (400 MHz, CDCl₃)	δ 7.53 – 7.37 (m, 12H), 7.33 – 7.28 (m, 8H), 7.22 – 7.12 (m, 5H), 3.55 – 3.36 (m, 3H), 2.92 – 2.85 (m, 2H), 2.52 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 143.9, 139.4, 133.1, 131.9 (d, JC-P = 2.6 Hz), 131.3 (d, JC-P = 90.4 Hz), 131.0 (d, JC-P = 9.1 Hz), 129.6, 128.7 (m, 9C), 128.0, 127.6, 77.4, 66.4, 29.2 (d, JC-P = 3.0 Hz, 2C), 28.3 (d, JC-P = 75.0 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.3
HRMS (ESI+)	Calculated for C₃₅H₃₃NO₃PS [M+H]⁺: 578.1913; found 578.1924

3-phenylprop-2-yn-1-yl 1-(aminodiphenylmethyl)-3-(diphenylphosphoryl)cyclobutane-1-carboxylate
Identifier	71
¹H NMR (400 MHz, CDCl₃)	δ 7.56 – 7.52 (m, 5H), 7.48 – 7.44 (m, 3H), 7.38 – 7.29 (m, 10H), 7.24 – 7.16 (m, 7H), 4.76 (s, 2H), 2.99 – 2.90 (m, 2H), 2.63 – 2.58 (m, 2H), 2.41 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.4, 145.9, 132.3 (d, JC-P = 99.9 Hz), 132.0, 131.8 (d, JC-P = 2.6 Hz), 131.1 (d, JC-P = 9.2 Hz), 128.9, 128.7 (d, JC-P = 11.5 Hz), 128.4, 128.0, 128.0, 127.2, 122.2, 86.7, 86.5, 65.7 (d, JC-P = 2.1 Hz), 56.9 (d, JC-P = 18.7 Hz), 53.5, 29.5 (d, JC-P = 3.9 Hz), 28.4 (d, JC-P = 76.2 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.7
HRMS (ESI+)	Calculated for C₃₉H₃₅NO₃P [M+H]⁺: 596.2349; found 596.2378

allyl 2,2,4,4-tetraphenyl-3-aza-2λ⁵-phosphabicyclo[3.1.1]hept-2-ene-5-carboxylate
Identifier	72
¹H NMR (400 MHz, CDCl₃)	δ 9.96 (s, 1H), 7.95 (dd, J = 13.5, 7.7 Hz, 4H), 7.68 (d, J = 7.7 Hz, 4H), 7.65 – 7.60 (m, 2H), 7.54 – 7.45 (m, 6H), 7.23 – 7.20 (m, 4H), 5.46 – 5.36 (m, 1H), 5.05 (d, J = 10.4 Hz, 1H), 4.98 (d, J = 17.2 Hz, 1H), (d, J = 10.4 Hz, 1H), 4.16 (d, J = 6.0 Hz, 2H), 3.19 – 3.06 (m, 3H), 2.90 – 2.83 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.2, 143.0 (d, JC-P = 5.1 Hz), 134.4 (d, JC-P = 3.0 Hz), 133.0 (d, JC-P = 11.1 Hz), 130.9, 129.7 (d, JC-P = 13.1 Hz), 129.0, 128.0, 127.8, 127.7, 122.6 (d, JC-P = 99.0 Hz), 119.2, 72.0 (d, JC-P = 5.1 Hz), 66.1, 54.9 (d, JC-P = 4.0 Hz), 31.3 (d, JC-P = 5.1 Hz, 2C), 23.8 (d, JC-P = 66.7 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 42.7
HRMS (ESI+)	Calculated for C₃₃H₃₂NO₂P [M+H]⁺: 505.2165; found 505.2174

allyl 1-(aminodiphenylmethyl)-3-(diphenylphosphoryl)cyclobutane-1-carboxylate
Identifier	73
¹H NMR (400 MHz, CDCl₃)	δ 7.76 – 7.59 (m, 4H), 7.58 – 7.54 (m, 2H), 7.50 – 7.45 (m, 4H), 7.39 – 7.28 (m, 10H), 5.67 – 5.57 (m, 1H), 5.20 – 5.16 (m, 2H), 4.48 (d, J = 5.9 Hz, 2H), 3.37 – 3.25 (m, 1H), 3.04 – 2.95 (m, 2H), 2.70 – 2.63 (m, 2H), 2.37 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.8, 146.0, 132.3 (d, JC-P = 94.8 Hz), 131.8, 131.6, 131.1 (d, JC-P = 9.3 Hz), 128.7 (d, JC-P = 11.5 Hz), 128.0, 127.9, 127.1, 118.8, 66.0, 65.6 (d, JC-P = 2.1 Hz), 57.0 (d, JC-P = 18.7 Hz), 29.5 (d, JC-P = 4.1 Hz), 28.4 (d, JC-P = 76.1 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.9
HRMS (ESI+)	Calculated for C₃₃H₃₃NO₃P [M+H]⁺: 522.2193; found 522.2231

((1r,3r)-3-(diphenylphosphoryl)cyclobutyl)(naphthalen-2-yl)methanone
Identifier	74
NMR reporting qualifier	The product was obtained as mixture of diastereoisomers d.r. = 2.1:1, only the major isomer is described
¹H NMR (400 MHz, CDCl₃)	δ 8.35 (s, 1H), 7.99 – 7.93 (m, 2H) 7.89 – 7.84 (m, 2H), 7.74 – 7.69 (m, 4H), 7.62 – 7.41 (m, 8H), 4.40 – 4.32 (m, 1H), 3.34 – 3.25 (m, 1H), 2.94 – 2.83 (m, 2H), 2.77 – 2.66 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 200.2, 135.8, 132.4, 132.3 (d, JC-P = 93.6 Hz), 132.2, 132.0 (d, JC-P = 3.0 Hz), 131.8, 131.1 (d, JC-P = 9.1 Hz), 130.4, 129.8, 128.9 (d, JC-P = 12.1 Hz), 128.7, 128.6, 127.9, 126.9, 124.2, 39.4 (d, JC-P = 9.1 Hz), 28.9 (d, JC-P = 74.0 Hz), 23.1 (d, JC-P = 5.1 Hz, 2C)
³¹P NMR (162 MHz, CDCl₃)	δ 33.5
HRMS (ESI+)	Calculated for C₂₇H₂₄O₂P [M+H]⁺: 411.1508; found 411.1534

((1r,3r)-3-(diphenylphosphoryl)cyclobutyl)(phenyl)methanone
Identifier	75
NMR reporting qualifier	The product was obtained as mixture of diastereoisomers d.r. = 2.3:1, only the major isomer is described
¹H NMR (400 MHz, CDCl₃)	δ 7.87 (d, J = 2.0 Hz, 2H) 7.72 – 7.67 (m, 4H), 7.56 – 7.42 (m, 9H), 4.22 – 4.14 (m, 1H), 3.30 – 3.22 (m, 1H), 2.88 – 2.76 (m, 2H), 2.69 – 2.58 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 200.1, 135.0, 133.4, 132.2 (d, JC-P = 93.0 Hz), 132.0 (d, JC-P = 3.0 Hz), 131.1 (d, JC-P = 9.4 Hz), 128.9 (d, JC-P = 7.7 Hz), 128.8, 128.6, 39.4 (d, JC-P = 9.3 Hz), 29.0 (d, JC-P = 74.4 Hz), 23.6 (d, JC-P = 5.2 Hz, 2C)
³¹P NMR (162 MHz, CDCl₃)	δ 33.3
HRMS (ESI+)	Calculated for C₂₃H₂₂O₂P [M+H]⁺: 361.1352; found 361.1397

ethyl 2,2,5,5-tetraphenyl-3-(propan-2-ylidene)-4,5-dihydro-3H-1,2λ⁵-azaphosphole-4-carboxylate
Identifier	76
¹H NMR (400 MHz, CDCl₃)	δ 10.32 (d, J = 11.1 Hz, 1H), 8.24 (dd, J = 14.3, 7.7 Hz, 2H), 7.76 – 7.66 (m, 1H), 7.68 – 7.58 (m, 4H), 7.54 (d, J = 7.7 Hz, 2H), 7.46 – 7.34 (m, 3H), 7.31 – 7.21 (m, 4H), 7.20 – 7.02 (m, 4H), 5.00 (d, J = 16.1 Hz, 1H), 3.72 – 3.61 (m, 1H), 3.49 – 3.36 (m, 1H), 2.19 (s, 3H), 1.87 (s, 2H), 0.73 (t, J = 7.1 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.9, 157.8 (d, JC-P = 11.2 Hz), 144.4, 141.0 (d, JC-P = 10.0 Hz), 134.9 (d, JC-P = 12.3 Hz), 134.1 (d, JC-P = 98.6 Hz), 134.1 (d, JC-P = 98.5 Hz), 133.7 (d, JC-P = 12.3 Hz), 129.3 (d, JC-P = 14.3 Hz), 129.0 (d, JC-P = 13.4 Hz), 128.7, 128.2, 127.7 (d, JC-P = 6.7 Hz), 127.3, 127.1, 122.9 (d, JC-P = 96.7 Hz), 121.9 (d, JC-P = 115.2 Hz) 119.8 (d, JC-P = 102.0 Hz), 73.6 (d, JC-P = 7.0 Hz), 61.6, 56.9 (d, JC-P = 14.3 Hz), 26.3 (d, JC-P = 8.3 Hz), 24.4 (d, JC-P = 13.3 Hz), 13.5
³¹P NMR (162 MHz, CDCl₃)	δ 39.1
HRMS (ESI+)	Calculated for C₃₃H₃₃NO₂P [M+H]⁺: 506.2240; found 506.2242

methyl 4-methyl-2,2,5,5-tetraphenyl-3-(propan-2-ylidene)-4,5-dihydro-3H-1,2λ⁵-azaphosphole-4-carboxylate
Identifier	77
¹H NMR (400 MHz, CDCl₃)	δ 9.98 (d, J = 9.4 Hz, 1H), 8.04 (dt, J = 14.4, 7.8 Hz, 4H), 7.65 (q, J = 8.4 Hz, 2H), 7.58 – 7.46 (m, 8H), 7.18 – 7.11 (m, 3H), 7.10 – 7.03 (m, 3H), 3.33 (s, 3H), 1.97 (s, 3H), 1.93 (s, 3H), 1.83 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.7 (d, JC-P = 6.0 Hz), 156.4 (d, JC-P = 11.1 Hz), 142.7, 141.7, 134.8 (d, JC-P = 98.3 Hz), 134.7 (d, JC-P = 97.6 Hz), 134.5 (d, JC-P = 3.0 Hz), 134.1 (d, JC-P = 3.1 Hz), 129.5 (d, JC-P = 13.5 Hz), 129.3 (d, JC-P = 13.9 Hz), 128.9, 128.0, 127.7 (d, JC-P = 1.6 Hz), 127.6, 127.3, 126.5 (d, JC-P = 99.0 Hz), 123.5 (d, JC-P = 98.1 Hz), 123.1 (d, JC-P = 99.4 Hz), 78.5 (d, JC-P = 5.9 Hz), 62.1 (d, JC-P = 16.2 Hz), 52.6, 28.5 (d, JC-P = 9.7 Hz), 25.5 (d, JC-P = 3.1 Hz), 24.3 (d, JC-P = 14.3 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 40.9
HRMS (ESI+)	Calculated for C₃₄H₃₅O₂P [M−HNO]⁺: 506.2371; found 506.2366

ethyl 3-(1-benzoylpiperidin-4-ylidene)-2,2,5,5-tetraphenyl-4,5-dihydro-3H-1,2λ⁵-azaphosphole-4-carboxylate
Identifier	78
¹H NMR (400 MHz, CDCl₃)	δ 10.41 (d, J = 11.2 Hz, 1H), 8.20 (dd, J = 14.7, 7.7 Hz, 2H), 7.78 – 7.70 (m, 1H), 7.65 (bs, 2H), 7.58 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 7.6 Hz, 2H), 7.48 – 7.35 (m, 7H), 7.35 – 7.16 (m, 8H), 7.14 – 7.02 (m, 3H), 5.04 (d, J = 15.4 Hz, 1H), 3.67 (bs, 2H), 3.54 – 3.27 (m, 3H), 3.00 (bs, 1H), 2.70 (bs, 2H), 2.31 (s, 2H), 1.37 – 1.80 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.9, 170.1, 158.6 (d, JC-P = 10.8 Hz), 143.99, 140.7 (d, JC-P = 10.4 Hz), 134.3 (d, JC-P = 137.0 Hz), 134.2 (d, JC-P = 137.0 Hz), 130.5, 129.6 (d, JC-P = 14.3 Hz), 129.1 (d, JC-P = 13.4 Hz), 128.8, 128.8, 128.3, 127.9 (d, JC-P = 8.8 Hz), 127.2, 127.1, 127.1, 122.6 (d, JC-P = 69.2 Hz), 121.5 (d, JC-P = 101.2 Hz), 120.5 (d, JC-P = 113.4 Hz), 73.6 (d, JC-P = 6.9 Hz), 61.9, 61.8, 56.0 (d, JC-P = 14.0 Hz), 45.9, 29.8, 13.6
³¹P NMR (162 MHz, CDCl₃)	δ 38.8
HRMS (ESI+)	Calculated for C₄₀H₄₂N₂O₃P [M+H]⁺: 651.2771; found 651.2845

methyl (E)-3-(1-(4-isobutylphenyl)ethylidene)-2,2,5,5-tetraphenyl-4,5-dihydro-3H-1,2λ⁵-azaphosphole-4-carboxylate
Identifier	79
Sample qualifier	The compound was obtained as a ca. 85:15 mixture of diastereoisomers
¹H NMR (400 MHz, CDCl₃)	δ 10.32 (d, J = 11.7 Hz, 0.15H), 10.22 (d, J = 11.7 Hz, 0.85H), 8.35 (dd, J = 14.3, 7.7 Hz, 0.30H), 7.78 (dd, J = 14.3, 7.7 Hz, 1.70H), 7.73 – 7.55 (m, 4H), 7.51 – 7.35 (m, 3H), 7.34 – 7.25 (m, 3H), 7.23 – 7.13 (m, 3H), 7.13 – 7.00 (m, 5H), 6.71 (d J = 7.7 Hz, 1.70H), 6.58 (d, J = 7.7 Hz, 1.70H), 5.16 (d, J = 16.2 Hz, 0.85H), 4.63 (d, J = 17.2 Hz, 0.15H), 3.79 – 3.69 (m, 1H), 3.57 – 3.47 (m, 1H), 2.53 (d, J = 7.2 Hz, 0.30H), 2.44 (s, 2.55H), 2.31 (d, J = 7.2 Hz, 1.70H), 2.09 (s, 0.45H), 1.81 – 1.59 (m, 2H), 0.93 (dd, J = 6.9, 2.6 Hz, 0.90H), 0.87 – 0.75 (m, 7.65H), 0.60 (t, J = 7.2 Hz, 0.45H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.9, 161.4 (d, JC-P = 10.5 Hz), 144.7, 142.9, 141.2 (d, JC-P = 9.8 Hz), 137.1 (d, JC-P = 6.9 Hz), 135.3 (d, JC-P = 12.5 Hz), 134.0 (d, JC-P = 12.3 Hz), 133.80 (d, JC-P = 136.1 Hz), 133.8 (d, JC-P = 135.9 Hz), 130.0, 129.2, 128.8, 128.4 (d, JC-P = 38.0 Hz), 128.2, 128.1, 127.7 (d, JC-P = 6.1 Hz), 127.5, 127.3, 127.2, 125.5, 125.3, 123.1 (d, JC-P = 92.3 Hz), 123.0 (d, JC-P = 108.7 Hz), 122.6 (d, JC-P = 101.7 Hz), 73.0 (d, JC-P = 6.3 Hz), 61.7, 61.2, 57.5 (d, JC-P = 14.5 Hz), 45.3, 45.0, 30.3, 30.2, 26.7(d, JC-P = 13.0 Hz), 22.5 (d, JC-P = 5.3 Hz), 22.3 (d, JC-P = 5.2 Hz), 13.7, 13.4
³¹P NMR (162 MHz, CDCl₃)	δ 39.8, 38.9
HRMS (ESI+)	Calculated for C₄₂H₄₃NO₂P [M−OH]⁺: 624.3026; found 624.3022

ethyl 5-(4-chlorophenyl)-5-(4-((1-isopropoxy-2-methyl-1-oxopropan-2-yl)oxy)phenyl)-2,2-diphenyl-3-(propan-2-ylidene)-4,5-dihydro-3H-1,2λ⁵-azaphosphole-4-carboxylate
Identifier	80
Diastereomer ratio	1:1
¹H NMR (400 MHz, CDCl₃)	δ 10.42 (d, J = 11.4 Hz, 0.42H), 10.34 (d, J = 10.8 Hz, 0.58H), 8.20 (dd, J = 14.3, 7.7 Hz, 2H), 7.78 – 7.70 (m, 1H), 7.68 – 7.56 (m, 4H), 7.55 – 7.35 (m, 8H), 7.33 – 7.28 (m, 1H), 7.04 (d, J = 8.2 Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 6.59 (d, J = 8.3 Hz, 1H), 5.03 (dq, J = 13.4, 6.6 Hz, 1H), 4.95 – 4.82 (m, 1H), 3.78 – 3.65 (m, 1H), 3.55 – 3.42 (m, 1H), 2.16 (s, 3H), 1.87 (s, 3H), 1.50 (dd, J = 14.9, 11.5 Hz, 6H), 1.28 – 1.16 (m, 6H), 0.83 (t, J = 7.1 Hz, 1.74H), 0.78 (t, J = 7.2 Hz, 1.26H)
¹³C NMR (101 MHz, CDCl₃)	δ 173.5 (d, JC-P = 28.2 Hz), 169.6, 155.2, 155.1, 135.1, 134.8, 134.4 (d, JC-P = 122.6 Hz), 134.3 (d, JC-P = 124.0 Hz), 133.7 (d, JC-P = 12.2 Hz), 133.7 (d, JC-P = 12.2 Hz), 129.4 (d, JC-P = 14.2 Hz), 129.1 (d, JC-P = 13.6 Hz), 129.1 (d, JC-P = 13.6 Hz), 129.0, 128.7 (d, JC-P = 9.2 Hz), 128.3, 128.2, 128.0, 122.5 (d, JC-P = 104.6 Hz), 120.5 (d, JC-P = 94.1 Hz), 118.9, 118.7, 79.2 (d, JC-P = 4.1 Hz), 72.8 (d, JC-P = 6.8 Hz), 69.1 (d, JC-P = 10.5 Hz), 61.8, 26.3 (d, JC-P = 8.7 Hz), 25.5 (d, JC-P = 15.9 Hz), 25.5, 24.4 (d, JC-P = 14.9 Hz), 21.7 (d, JC-P = 3.9 Hz), 13.70 (d, JC-P = 21.7 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 39.0
HRMS (ESI+)	Calculated for C₄₀H₄₄ClNO₅P [M+H]⁺: 684.2640; found 684.2729

ethyl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)but-2-enoate
Identifier	81
¹H NMR (400 MHz, CDCl₃)	δ 7.55 – 7.38 (m, 14H), 7.20 – 7.10 (m, 6H), 3.78 (bs, 2H), 3.62 (q, J = 7.1 Hz, 2H), 1.75 (d, J = 13.4 Hz, 3H), 0.97 (t, J = 7.1 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.9 (d, JC-P = 21.5 Hz), 162.5, 147.4, 132.0 (d, JC-P = 9.6 Hz), 131.9 (d, JC-P = 2.8 Hz), 128.7, 128.5, 128.4, 127.5, 126.9, 126.4 (d, JC-P = 85.3 Hz), 66.4 (d, JC-P = 5.4 Hz), 61.0, 21.5 (d, JC-P = 13.7 Hz), 13.8
³¹P NMR (162 MHz, CDCl₃)	δ 30.2
HRMS (ESI+)	Calculated for C₃₁H₃₁NO₃P [M+H]⁺: 496.2036; found 496.2033

ethyl (E)-3-(diphenylphosphoryl)-4-phenylbut-3-enoate
Identifier	82
¹H NMR (400 MHz, CDCl₃)	δ 7.85 – 7.71 (m, 4H), 7.60 – 7.52 (m, 2H), 7.52 – 7.43 (m, 4H), 7.45 (s, 1H), 7.42 – 7.31 (m, 5H), 3.81 (q, J =7.1 Hz, 2H), 3.54 (d, J = 15.7 Hz, 2H), 1.02 (t, J = 7.1 Hz, 3H)
¹³C NMR (100 MHz, CDCl₃)	δ 170.2 (d, JC-P = 2.7 Hz), 146.7 (d, JC-P = 10.5 Hz), 135.3 (d, JC-P = 17.7 Hz), 132.4 (d, JC-P = 9.8 Hz), 132.2 (d, JC-P = 2.8 Hz), 131.4 (d, JC-P = 103.1 Hz), 129.1, 128.9, 128.7, 128.6, 128.2 (d, JC-P = 98.8 Hz), 61.1, 34.1 (d, JC-P = 11.3 Hz), 14.0
³¹P NMR (162 MHz, CDCl₃)	δ 32.2
HRMS (ESI+)	Calculated for C₂₄H₂₄O₃P [M+H]⁺: 391.1458; found 391.1455

ethyl (E)-3-(diphenylphosphoryl)pent-3-enoate
Identifier	83
¹H NMR (400 MHz, CDCl₃)	δ 7.76 – 7.67 (m, 4H), 7.70 – 7.49 (m, 2H), 7.50 – 7.41 (m, 4H), 6.51 (dq, J = 20.5, 6.9 Hz, 1H), 3.90 (q, J = 7.1 Hz, 2H), 3.35 (d, J = 14.2 Hz, 2H), 1.87 (dd, J = 6.9, 2.8 Hz, 3H), 1.07 (t, J = 7.2 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.0 (d, JC-P = 3.4 Hz), 146.0 (d, JC-P = 10.0 Hz), 132.5 (d, JC-P = 8.2 Hz), 132.3 (d, JC-P = 9.8 Hz), 132.0, 131.5 (d, JC-P = 103.6 Hz), 128.6 (d, JC-P = 12.0 Hz), 127.8 (d, JC-P = 102.8 Hz), 61.0, 32.4 (d, JC-P = 12.6 Hz), 15.7 (d, JC-P = 15.5 Hz), 14.1
³¹P NMR (162 MHz, CDCl₃)	δ 31.8
HRMS (ESI+)	Calculated for C₁₉H₂₂O₃P [M+H]⁺: 329.1301; found 329.1392

3-(diphenylphosphoryl)-1,3-diphenylpropan-1-one
Identifier	89
¹H NMR (400 MHz, CDCl₃)	δ 8.01 – 7.96 (m, 2H), 7.85 – 7.83 (m, 2H), 7.53 – 7.44 (m, 7H), 7.39 – 7.32 (m, 5H), 7.25 – 7.22 (m, 1H), 7.16 – 7.09 (m, 3H), 4.47 (ddd, J = 9.7, 6.9, 2.3 Hz, 1H), 4.01 (ddd, J = 18.1, 10.3, 4.4 Hz, 1H), 3.39 (ddd, J = 18.1, 11.2, 2.4 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 196.8 (d, JC-P = 13.4 Hz), 136.6, 136.1 (d, JC-P = 5.6 Hz), 133.5, 132.2 (d, JC-P = 2.7 Hz), 131.8 (d, JC-P = 100.3 Hz), 131.6 (d, JC-P = 94.6 Hz), 131.6 (d, JC-P = 2.8 Hz), 131.5 (d, JC-P = 8.4 Hz), 131.1 (d, JC-P = 8.8 Hz), 130.0 (d, JC-P = 5.7 Hz), 129.1 (d, JC-P = 11.3 Hz), 128.7, 128.5 (d, JC-P = 1.8 Hz), 128.3, 128.2 (d, JC-P = 10.4 Hz), 127.2 (d, JC-P = 2.4 Hz), 41.2 (d, JC-P = 69.2 Hz), 39.2
³¹P NMR (162 MHz, CDCl₃)	δ 34.3
HRMS (ESI+)	Calculated for C₂₇H₂₄O₂P [M+H]⁺: 411.1508; found 411.1591

3-(diphenylphosphoryl)-3-(2-hydroxyphenyl)-1-phenylpropan-1-one
Identifier	90
¹H NMR (400 MHz, CDCl₃)	δ 11.89 (s, 1H, OH), 8.00 – 7.95 (m, 2H), 7.72 – 7.68 (m, 2H), 7.58 – 7.34 (m, 10H), 7.17 – 7.11 (m, 3H), 6.89 – 6.81 (m, 2H), 4.42 – 4.39 (m, 1H), 4.07 – 3.99 (m, 1H), 3.43 (dd, J = 15.9, 10.9 Hz, 1H)
¹³C NMR (400 MHz, CDCl₃)	δ 202.7 (d, JC-P= 13.3 Hz), 162.3, 136.8, 132.3 (d, JC-P= 2.5 Hz), 131.7 (d, JC-P= 2.8 Hz), 131.5 (d, JC-P= 99.0 Hz), 131.3 (d, JC-P= 99.0 Hz), 131.4 (d, JC-P = 8.5 Hz), 131.1 (d, JC-P = 8.9 Hz), 130.1, 129.9 (d, JC-P= 5.6 Hz), 129.2 (d, JC-P = 11.3 Hz), 128.6, 128.5, 128.3 (d, JC-P = 11.9 Hz), 127.4 (d, JC-P = 2.4 Hz), 119.2, 118.5, 41.1 (d, JC-P = 68.8 Hz), 38.6
³¹P NMR (162 MHz, CDCl₃)	δ 34.2
HRMS (ESI+)	Calculated for C₂₇H₂₄O₃P [M+H]⁺: 427.1458; found 427.1534

3-(diphenylphosphoryl)-3-(3-hydroxyphenyl)-1-phenylpropan-1-one
Identifier	91
¹H NMR (400 MHz, CDCl₃)	δ 9.70 (s, 1H), 8.00 – 7.94 (m, 2H)7.78 (s, 1H), 7.56 – 7.48 (m, 5H), 7.41 (d, J = 8.0 Hz, 2H), 7.35 – 7.31 (m, 1H), 7.18 – 7.15 (m, 2H), 7.08 (t, J = 7.6 Hz, 2H), 7.01 (t, J = 7.7 Hz, 1H), 6.70 (t, J = 8.7 Hz, 2H), 4.54 – 4.50 (m, 1H), 3.98 – 3.90 (m, 1H), 3.39 – 3.32 (m, 1H)
¹³C NMR (400 MHz, DMSO-d₆)	δ 196.9 (d, JC-P = 13.8 Hz), 156.9, 137.66 (d, JC-P = 5.2 Hz), 136.3, 133.7, 132.5 (d, JC-P = 82.3 Hz), 131.9 (d, JC-P = 88.2 Hz), 132.2, 131.7, 131.1 (d, JC-P = 8.8 Hz), 131.0 (d, JC-P = 8.6 Hz), 129.1 (d, JC-P = 11.1 Hz), 129.0, 129.0 (d, JC-P = 9.3 Hz), 128.1, 128.4 (d, JC-P = 11.3 Hz), 120.9, 116.8 (d, JC-P = 5.3 Hz), 114.0, 40.4, (d, JC-P = 68.0 Hz) 38.3
³¹P NMR (162 MHz, CDCl₃)	δ 38.0
HRMS (ESI+)	Calculated for C₂₇H₂₄O₃P [M+H]⁺: 427.1458; found 427.1487

1-(1-azabicyclo[1.1.0]butan-3-yl)-3-(diphenylphosphoryl)-3-phenylpropan-1-one
Identifier	92
¹H NMR (400 MHz, CDCl₃)	δ 7.93 (t, J = 8.3 Hz, 2H), 7.62 – 7.49 (m, 3H), 7.41 (dd, J = 11.1, 7.7 Hz, 2H), 7.36 – 7.09 (m, 8H), 4.24 (td, J = 7.3, 3.5 Hz, 1H), 3.47 (ddd, J = 18.2, 10.4, 4.7 Hz, 1H), 3.03 (ddd, J = 18.2, 10.8, 2.7 Hz, 1H), 2.82 (s, 2H), 1.43 (d, J = 7.1 Hz, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 203.6 (d, JC-P = 13.8 Hz), 135.5 (d, JC-P = 5.8 Hz), 132.3 (d, JC-P = 2.9 Hz), 131.6 (d, JC-P = 2.9 Hz), 131.5 (d, JC-P = 101.0 Hz), 131.4 (d, JC-P = 8.7 Hz), 131.3 (d, JC-P = 94.5 Hz), 131.1 (d, JC-P = 9.1 Hz), 129.9 (d, JC-P = 5.8 Hz), 129.2 (d, JC-P = 11.6 Hz), 128.5 (d, JC-P = 2.2 Hz), 128.2 (d, JC-P = 12.0 Hz), 127.4 (d, JC-P = 2.5 Hz), 55.7 (d, JC-P = 27.2 Hz), 41.0 (d, JC-P = 68.7 Hz), 39.7, 30.2 (d, JC-P = 1.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 33.7
HRMS (ESI+)	Calculated for C₃₁H₂₇NOP [M+H]⁺: 388.1461; found 388.1477

3-(diphenylphosphoryl)-3-phenylpropanoic acid
Identifier	93
¹H NMR (400 MHz, CDCl₃)	δ 7.99 – 7.94 (m, 2H), 7.60 – 7.54 (m, 3H), 7.45 – 7.40 (m, 2H), 7.33 – 7.31 (m, 3H), 7.23 – 7.15 (m, 5H), 6.08 (bs, 1H, intra or intermolecular COOH H-bonding), 5.11 (bs, 1H, intra or intermolecular COOH H-bonding), 4.22 – 4.17 (m, 1H), 3.11 – 3.03 (m, 1H), 2.87 – 2.80 (m, 1H)
¹³C NMR (400 MHz, DMSO-d₆)	δ 170.9 (d, JC-P= 16.3 Hz), 135.9 (d, JC-P = 5.5 Hz), 132.7 (d, JC-P = 92.5 Hz), 132.3 (d, JC-P = 97.9 Hz), 131.7 (d, JC-P = 2.6 Hz), 131.2 (d, JC-P = 2.6 Hz), 130.8 (d, JC-P = 8.6 Hz), 130.7 (d, JC-P = 8.8 Hz), 129.7 (d, JC-P = 5.5 Hz), 128.8 (d, JC-P = 11.0 Hz), 128.1 (d, JC-P = 11.5 Hz), 127.7, 126.6 (d, JC-P = 2.1 Hz), 41.1 (d, JC-P = 68.1 Hz), 34.9
³¹P NMR (162 MHz, CDCl₃)	δ 33.9
HRMS (ESI+)	Calculated for C₂₁H₁₉NaO₃P [M+Na]⁺: 373.0964; found 373.1202

methyl (Z)-2-((diphenylphosphoryl)methyl)-3-phenylacrylate
Identifier	95
¹H NMR (400 MHz, CDCl₃)	δ 7.83 (d, J = 4.6 Hz, 1H), 7.79 – 7.74 (m, 4H), 7.65 (d, J = 7.1 Hz, 2H), 7.57 – 7.49 (m, 2H), 7.46 – 7.42 (m, 4H), 7.37 – 7.30 (m, 3H), 3.74 (d, J = 14.5 Hz, 2H), 3.44 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.0, 142.8 (d, JC-P = 8.9 Hz), 134.7 (d, JC-P = 3.0 Hz), 132.7 (d, JC-P = 99.2 Hz), 131.8 (d, JC-P = 2.8 Hz), 131.3 (d, JC-P = 9.3 Hz), 129.5, 129.0, 128.6, 128.4 (d, JC-P = 11.8 Hz), 123.7 (d, JC-P = 9.8 Hz), 52.0, 30.87 (d, JC-P = 67.5 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 29.3
HRMS (ESI+)	Calculated for C₂₃H₂₂O₃P [M+H]⁺: 377.1301; found 377.1344

methyl 2-((diphenylphosphoryl)methyl)-3-hydroxy-3-phenylpropanoate
Identifier	98
Diastereomer ratio	2.3:1
¹H NMR (400 MHz, CDCl₃)	δ 7.75 – 7.63 (m, 6H, overlapped), 7.53 – 7.42 (m, 9H, overlapped), 7.31 – 7.16 (m, 15H), 5.18 (d, J = 4.7 Hz, 1H, major diastereoisomer), 4.98 (d, J = 12.3 Hz, 1H, major diastereoisomer), 4.96 – 4.95 (m, 0.50H, minor diastereoisomer), 4.79 (d, J = 12.3 Hz, 1H, major diastereoisomer), 4.73 (d, J = 12.4 Hz, 0.50H, minor diastereoisomer), 4.65 (d, J = 12.4 Hz, 0.50H, minor diastereoisomer), 3.37 – 3.30 (m, 1H, major diastereoisomer), 3.18 – 3.13 (m, 0.50H, minor diastereoisomer), 2.82 – 2.73 (m, 1.50H, overlapped), 2.52 – 2.43 (m, 1.50H, overlapped)
¹³C NMR (600 MHz, CDCl₃)	δ 172.8 (d, JC-P = 6.5 Hz, minor diastereoisomer), 172.5 (d, JC-P= 9.4 Hz, major diastereoisomer), 141.1 (minor diastereoisomer), 140.6 (major diastereoisomer), 135.1, 132.7 – 127.8 (m, mixture of minor and major diastereoisomers, 20C), 126.5 (minor diastereoisomer), 126.2 (major diastereoisomer), 75.1 (d, JC-P = 7.6 Hz, minor diastereoisomer), 74.5 (d, JC-P = 7.1 Hz), 67.0 (major diastereoisomer), 66.8 (minor diastereoisomer), 48.0 (minor diastereoisomer), 46.8 (major diastereoisomer), 28.9 (d, JC-P = 70.8 Hz, minor diastereoisomer), 27.9 (d, JC-P = 71.3 Hz, major diastereoisomer)
³¹P NMR (162 MHz, CDCl₃)	δ 32.8, 32.7
HRMS (ESI+)	Calculated for C₂₉H₂₈O₄P [M+H]⁺: 471.1720; found 471.1739

benzyl 2-((diphenylphosphoryl)methyl)-3-hydroxy-3-(4-(trifluoromethyl)phenyl)propanoate
Identifier	99
Diastereomer ratio	2.4:1
NMR reporting qualifier	Only the major isomer is described
¹H NMR (400 MHz, CDCl₃)	δ 7.76 (dd, J = 11.2, 7.7 Hz, 2H), 7.68 (dd, J = 11.5, 7.8 Hz, 2H), 7.57 – 7.44 (m, 9H), 7.32 – 7.27 (m, 4H), 7.14 (d, J = 4.9 Hz, 2H), 5.40 (d, J = 8.8 Hz, 1H), 5.30 (bs, 1H), 5.00 (d, J = 12.0 Hz, 1H), 4.79 (d, J = 12.3 Hz, 1H), 3.39 – 3.30 (m, 1H), 2.81 – 2.74 (m, 1H), 2.49 (td, J = 15.2, 14.8, 7.9 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.4, 145.0, 134.9, 133.3 (d, JC-P = 93.0 Hz), 132.9 (d, JC-P = 100.0 Hz), 132.5 – 132.4 (m, 2C), 131.34 (d, JC-P = 9.4 Hz), 130.69 (d, JC-P = 9.7 Hz), 130.0 (q, JC-F = 30.0 Hz), 129.09 (d, JC-P = 11.8 Hz), 129.04 (d, JC-P = 11.9 Hz), 128.8, 128.7, 128.3 – 128.1 (m, 2C), 127.5 (q, JC-F = 217.0 Hz), 126.7, 125.4 – 125.3 (m, 2C), 73.1, 68.0, 46.8, 22.8 (d, JC-P = 73.0 Hz)
¹⁹F NMR ( MHz, CDCl₃)	δ −62.48
³¹P NMR (162 MHz, CDCl₃)	δ 33.1
HRMS (ESI+)	Calculated for C₃₀H₂₇F₃O₄P [M+H]⁺: 539.1594; found 539.1633

(2-(aminodiphenylmethyl)phenyl)diphenylphosphine oxide
Identifier	101
¹H NMR (400 MHz, CDCl₃)	δ 7.50 – 7.40 (m, 3H), 7.39 – 7.27 (m, 10H), 7.18 (t, J = 7.5 Hz, 1H), 7.14 – 7.05 (m, 9H), 6.94 – 6.86 (m, 1H), 3.91 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 155.36 (d, JC-P = 5.8 Hz), 147.79, 136.83 (d, JC-P = 14.2 Hz), 134.27 (d, JC-P = 106.4 Hz), 132.28 (d, JC-P = 10.2 Hz), 131.71 (d, JC-P = 9.4 Hz), 131.28 (d, JC-P = 2.5 Hz), 130.86 (d, JC-P = 2.9 Hz), 129.69 (d, JC-P = 97.4 Hz), 128.66, 128.34 (d, JC-P = 12.4 Hz), 127.63, 126.76, 125.63 (d, JC-P = 13.8 Hz), 68.37 (d, JC-P = 2.5 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 34.7
HRMS (ESI+)	Calculated for C₃₁H₂₇NOP [M+H]⁺: 460.1825; found 460.1825

(2-(diphenylphosphoryl)cyclopentyl)(phenyl)methanone
Identifier	103
¹H NMR (400 MHz, CDCl₃)	δ 7.90 – 7.80 (m, 6H), 7.54 – 7.48 (m, 4H), 7.44 – 7.38 (m, 5H), 3.42 – 3.24 (m, 4H), 1.92 – 1.83 (m, 2H), 1.73 – 1.66 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 197.6 (d, JC-P = 11.0 Hz), 136.3, 133.7, 132.1 (d, JC-P = 96.5 Hz), 131.9 (d, JC-P = 95.9 Hz), 132.0 (t, JC-P = 3.0 Hz, 2C), 131.10 (d, JC-P = 7.1 Hz), 131.0 (d, JC-P = 6.9 Hz), 129.0 (d, JC-P = 11.2 Hz), 128.9 (d, JC-P = 11.3 Hz), 128.8, 128.2, 44.5, 31.1 (d, JC-P = 73.0 Hz), 31.0, 30.7 (d, JC-P = 10.2 Hz), 27.5
³¹P NMR (162 MHz, CDCl₃)	δ 36.8
HRMS (ESI+)	Calculated for C₂₄H₂₄O₂P [M+H]⁺: 375.1508; found 375.1365

3-(diphenylphosphoryl)-2-phenylpropanoic acid
Identifier	107
¹H NMR (400 MHz, DMSO-d₆)	δ 7.80 – 7.73 (m, 2H), 7.69 – 7.64 (m, 2H), 7.55 – 7.39 (m, 6H), 7.25 – 7.23 (m, 2H), 7.19 – 7.12 (m, 3H), 6.75 (br s, 1H), 3.93 – 3.86 (m, 1H), 3.26 – 3.17 (m, 1H), 2.75 – 2.68 (m, 1H)
¹³C NMR (400 MHz, DMSO-d₆)	δ 173.2 (d, JC-P = 6.4 Hz), 141.0 (d, JC-P = 8.9 Hz), 134.2 (d, JC-P = 97.0 Hz), 133.8 (d, JC-P = 96.7 Hz), 131.5 (d, JC-P = 2.7 Hz), 131.2 (d, JC-P = 2.4 Hz), 130.4 (d, JC-P = 9.4 Hz), 130.4 (d, JC-P = 9.3 Hz), 128.5 (d, JC-P = 11.2 Hz), 128.4 (d, JC-P = 11.1 Hz), 128.0, 127.7, 126.6, 44.3, 32.1 (d, JC-P = 70.6 Hz)
³¹P NMR (162 MHz, DMSO-d₆)	δ 28.3
HRMS (ESI+)	Calculated for C₂₁H₁₈O₃P [M−H]⁺: 349.0999; found 349.1007

(8S,9S,10R,13R)-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 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	108
¹H NMR (400 MHz, CDCl₃)	δ 7.81 – 7.36 (m, 16H), 7.23 – 7.08 (m, 4H), 5.16 – 5.09 (m, 1H), 4.22 – 4.11 (m, 1H), 3.80 – 3.70 (m, 1H), 2.99 – 2.91 (m, 1H), 2.55 – 2.48 (m, 2H), 2.32 (bs, 2H), 1.99 – 0.94 (m, 33H), 0.87 – 0.85 (m, 6H), 0.66 (s, 3H)
¹³C NMR (150 MHz, CDCl₃)	δ173.4, 144.8, 139.8, 133.6 (d, JC-P = 98.7 Hz), 132.4 – 131.8 (m, 3C), 131.4 (d, JC-P = 101.2 Hz), 131.5 – 131.2 (m, 3C), 130.9 – 130.5 (m, 3C), 129.0 – 128.4 (m, 5C), 127.9 (2C), 127.0, 126.8, 126.6 (3C), 122.2, 74.5, 64.0, 56.5 (d, JC-P = 81.4 Hz), 50.0, 46.3, 42.4, 40.6, 40.5, 40.3, 40.2, 40.1, 39.9, 39.8, 39.6, 36.5 (d, JC-P = 16.0 Hz), 36.2, 35.8, 31.9, 28.3, 28.1, 26.8, 24.3, 23.9, 22.9, 22.6, 21.0, 19.2, 18.8, 11.9
³¹P NMR (162 MHz, CDCl₃)	δ 30.5

(2R,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl 3-amino-2-((diphenylphosphoryl)methyl)-3,3-diphenylpropanoate
Identifier	109
Sample qualifier	Single diastereoisomer
¹H NMR (400 MHz, CDCl₃)	δ 7.70 – 7.64 (m, 4H), 7.58 – 7.55 (m, 1H), 7.47 – 7.43 (m, 6H), 7.34 – 7.27 (m, 15H), 7.22 – 7.08 (m, 13), 6.94 – 6.91 8m, 1H), 6.01 (d, J = 3.0 Hz, 1H), 5.00 (d, J = 10.9 Hz, 1H), 4.84 (d, J = 11.0 Hz, 2H), 4.78 (d, J = 11.1 Hz, 1H), 4.54 (d, J = 12.1 Hz, 1H), 4.46 (d, J = 12.1 Hz, 1H), 4.42 (d, J = 11.1 Hz, 1H), 4.34 (d, J = 12.1 Hz, 1H), 4.07 (t, J = 11.3 Hz, 1H), 3.75 – 3.70 (m, 1H), 3.62 – 3.55 (m, 2H), 3.42 (d, J = 9.9 Hz, 1H), 3.30 (d, J = 10.7 Hz, 1H), 2.97 (q, J = 13.3 Hz, 1H), 2.49 (d, J = 9.9 Hz, 1H), 2.27 (dd, J = 14.6, 9.1 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.4, 145.2, 145.0, 138.9, 138.7, 138.1, 138.0, 133.0 (d, JC-P= 99.5 Hz), 132.0 – 131.9 (m, 2C), 131.9 (d, JC-P = 98.9 Hz), 131.68 (d, JC-P = 9.5 Hz), 130.80 (d, JC-P = 9.4 Hz), 128.7, 128.6, 128.5, 128.32 (d, JC-P = 5.1 Hz), 128.2, 128.2 (d, J = 5.1 Hz), 127.9, 127.6, 127.6, 127.5, 127.4, 127.4, 127.0, 126.8, 126.2, 126.0, 91.5, 81.3, 78.3, 76.5, 75.5, 74.7, 73.4, 72.3, 71.8, 67.9, 63.7 (d, JC-P = 12.3 Hz) 47.3, 29.3 (d, JC-P = 70.2 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.6
HRMS (ESI+)	Calculated for C₆₂H₆₂NO₈P [M+H]⁺: 979.4208; found 979.4221

(E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)-N-methyl-N-(3-phenyl-3-(4-(trifluoromethyl)phenoxy)propyl)acrylamide
Identifier	110
NMR reporting qualifier	The compound was observed as a mixture of rotamers in CDCl₃ at 298 K. Signals were not distinguishable and are reported together in the ¹H and ¹³C NMR
¹H NMR (400 MHz, CDCl₃)	δ 7.81 – 7.17 (m, 21H), 7.15 – 6.97 (m, 6H), 6.88 (d, J = 8.5 Hz, 0.5H), 6.79 (d, J = 8.7 Hz, 1.5H), 6.23 (d, J = 20.2 Hz, 0.4H), 6.10 (d, J = 20.0 Hz, 0.6H), 5.09 – 5.01 (m, 0.2H), 5.00 – 4.86 (m, 0.8H), 4.42 – 4.29 (m, 0.2H), 3.39 (bs, 0.8H), 3.14 – 2.54 (m, 6H), 2.47 (s, 0.4H), 2.44 (s, 0.6H), 1.55 (bs, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.3 (d, JC-P = 18.7 Hz), 170.1 (d, JC-P = 18.9 Hz), 165.9, 165.1, 160.4, 160.2, 140.5, 140.4, 132.2 (d, JC-P = 109.2 Hz), 132.0 – 131.7 (m), 131.3 – 130.7 (m), 129.7, 129.1, 128.8, 129.1 – 128.2 (m), 128.2 – 128.0 (m), 127.9 – 127.3 (m), 127.1 – 126.6 (m), 125.9 – 125.4 (m), 123.5 (d, JC-P = 9.9 Hz), 123.1 (d, JC-P = 9.1 Hz), 122.9, 122.5, 121.3 (d, JC-P = 94.8 Hz), 120.9 (d, JC-P = 94.5 Hz), 116.0, 115.8, 78.5, 77.9, 66.7 (d, JC-P = 5.4 Hz), 66.6 (d, JC-P = 5.8 Hz), 48.2, 47.6, 44.2, 37.5, 37.1, 35.1, 32.1, 31.8
³¹P NMR (162 MHz, CDCl₃)	δ 19.3, 18.4
¹⁹F NMR (377 MHz, CDCl₃)	δ −62.1, −62.1
HRMS (ESI+)	Calculated for C₄₅H₄₁F₃N₂O₃P [M+H]⁺: 745.2802; found 745.2855

2-((2-(6-methoxynaphthalen-2-yl)propanoyl)oxy)ethyl 3-(diphenylphosphoryl)-2-methylpropanoate
Identifier	111
Diastereomer ratio	1:1
¹H NMR (400 MHz, CDCl₃)	δ 7.74 – 7.62 (m, 7H), 7.54 – 7.41 (m, 6H), 7.37 – 7.34 (m, 1H), 7.13 – 7.08 (m, 2H), 4.27 – 3.97 (m, 4H), 3.90 (s, 3H), 3.84 (q, J = 7.0 Hz, 1H), 2.93 – 2.75 (m, 2H), 2.23 – 2.14 (m, 1H), 1.55 (d, J = 7.2 Hz, 3H), 1.15 – 1.12 (m, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.3 (d, JC-P = 3.0 Hz), 175.1 (d, JC-P = 2.9 Hz), 174.5, 157.8,135.5, 135.4, 133.9, 133.5 (d, JC-P = 99.6 Hz), 132.4 (d, JC-P = 101.0 Hz), 132.0, 131.9, 131.1 (d, JC-P = 9.5 Hz), 130.8 (d, JC-P = 9.4 Hz), 129.4, 129.1, 128.9 (d, JC-P = 7.1 Hz), 128.8 (d, JC-P = 7.2 Hz), 127.4, 127.3, 126.3, 126.2, 126.1, 126.0, 119.2, 105.7, 62.6, 62.4, 55.5, 45.5, 45.4, 33.8 (d, JC-P = 2.5 Hz), 32.9 (d, JC-P = 71 Hz), 32.8 (d, JC-P = 71 Hz), 19.1, 19.0, 18.6 (d, JC-P = 13.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.1
HRMS (ESI+)	Calculated for C₃₂H₃₄O₆P [M+H]⁺: 545.2088; found 545.2096

(E)-2-(aminodiphenylmethyl)-1-(4-(2-chlorodibenzo[b,f][1,4]oxazepin-11-yl)piperazin-1-yl)-3-(diphenylphosphoryl)prop-2-en-1-one
Identifier	112
¹H NMR (400 MHz, CDCl₃)	δ 7.71 (dd, J = 12.0, 7.9 Hz, 2H), 7.60 – 7.54 (m, 2H), 7.53 – 7.32 (m, 12H), 7.25 – 7.17 (m, 4H), 7.15 – 7.07 (m, 6H), 7.05 – 6.98 (m, 1H), 6.21 (d, J = 19.6 Hz, 1H), 3.77 – 2.90 (m, 10H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.1 (d, JC-P = 18.9 Hz), 164.0, 159.4, 158.5, 151.8, 147.8, 144.8, 139.9, 134.2 (d, JC-P = 107.5 Hz), 133.0, 132.0 (d, JC-P = 2.9 Hz), 131.8 (d, JC-P = 2.9 Hz), 131.1 (d, JC-P = 9.8 Hz), 130.9 (d, JC-P = 9.4 Hz), 130.5, 129.0, 128.9, 128.9, 128.6 (d, JC-P = 12.4 Hz), 128.3, 128.0, 127.8, 127.7, 127.7, 127.2, 126.8, 126.00, 125.1, 124.8, 123.0, 122.3 (d, JC-P = 94.1 Hz), 120.3, 66.8 (d, JC-P = 5.1 Hz), 46.4, 40.9
³¹P NMR (162 MHz, CDCl₃)	δ 19.3
HRMS (ESI+)	Calculated for C₄₅H₃₉ClN₄O₃P [M+H]⁺: 749.2443; found 749.2464

5′,5′-dimethylhexahydro-1H-spiro[pentalene-2,2′-[1,3]dioxan]-5-yl (E)-2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)acrylate
Identifier	113
¹H NMR (400 MHz, CDCl₃)	δ 7.60 (dd, J = 12.0, 7.2 Hz, 4H), 7.51 – 7.45 (m, 2H), 7.44 – 7.35 (m, 8H), 7.20 – 7.10 (m, 6H), 6.88 (d, J = 19.6 Hz, 1H), 4.94 (bs, 1H), 3.42 (d, J = 17.2 Hz, 4H), 2.58 (bs, 2H), 2.34 (bs, 2H), 2.11 – 2.01 (m, 2H), 1.62 – 1.37 (m, 6H), 0.93 (s, 6H)
¹³C NMR (101 MHz, CDCl₃)	δ 168.3 (d, JC-P = 20.5 Hz), 163.6, 146.4, 134.1 (d, JC-P = 108.7 Hz), 131.7 (d, JC-P = 2.7 Hz), 130.9 (d, JC-P = 9.6 Hz), 128.7 (d, JC-P = 12.3 Hz), 128.0 (d, JC-P = 96.3 Hz), 127.8 (d, JC-P = 9.9 Hz), 127.0, 110.2, 80.2, 72.1 (d, JC-P = 11.6 Hz), 66.4, 66.4, 39.9, 38.8, 38.3, 30.2, 22.6
³¹P NMR (162 MHz, CDCl₃)	δ 19.6
HRMS (ESI+)	Calculated for C₄₁H₄₅NO₅P [M+H]⁺: 662.3030; found 662.3043

2,5-dioxopyrrolidin-1-yl (Z)-4-(12-(aminodiphenylmethyl)-11-(diphenylphosphoryl)dibenzo[b,f]azocin-5(6H)-yl)-4-oxobutanoate
Identifier	114
NMR reporting qualifier	The NH₂ proton were impossible to described
¹H NMR (400 MHz, CDCl₃)	δ 7.79 (dd, J = 12.2, 7.5 Hz, 2H), 7.46 – 7.29 (m, 10H), 7.28 – 7.12 (m, 8H), 6.78 – 6.51 (m, 7H), 6.39 (d, J = 7.7 Hz, 1H), 4.50 (d, J = 13.6 Hz, 1H), 4.38 (d, J = 13.6 Hz, 1H), 2.95 (dd, J = 16.8, 6.2 Hz, 2H), 2.81 (s, 4H), 2.51 – 2.38 (m, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.0, 169.1, 168.5, 164.1 (d, JC-P = 5.3 Hz), 147.6, 146.7, 142.3 (d, JC-P = 12.4 Hz), 141.9 (d, JC-P = 12.6 Hz), 137.4 (d, JC-P = 1.7 Hz), 135.8 (d, JC-P = 87.6 Hz), 134.8 (d, JC-P = 4.2 Hz), 134.5 (d, JC-P = 106.4 Hz), 132.6 (d, JC-P = 10.0 Hz), 132.2 (d, JC-P = 8.8 Hz), 131.4 (d, JC-P = 2.6 Hz), 131.4 (d, JC-P = 2.9 Hz), 130.6 (d, JC-P = 4.9 Hz), 129.4, 129.4 (d, JC-P = 2.5 Hz), 129.2, 128.6, 128.1, 128.0, 128.0, 127.9, 127.8, 127.8, 127.4 (d, JC-P = 17.9 Hz), 127.1 (d, JC-P = 8.1 Hz), 126.5, 70.0 (d, JC-P = 3.1 Hz), 54.3, 29.5, 26.9, 25.7
³¹P NMR (162 MHz, CDCl₃)	δ 28.1
HRMS (ESI+)	Calculated for C₄₈H₄₁N₃O₆P [M+H]⁺: 786.2727; found 786.2793

(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 (1r,3R)-1-(aminodiphenylmethyl)-3-(diphenylphosphoryl)cyclobutane-1-carboxylate
Identifier	115
¹H NMR (400 MHz, CDCl₃)	δ 7.58 – 7.45 (m, 8H), 7.41 – 7.36 (m, 4H), 7.30 – 7.28 (m, 4H), 7.25 – 7.17 (m, 4H), 5.26 – 5.24 (m, 1H), 4.49 – 4.41 (m, 1H), 3.26 – 3.16 (m, 1H), 2.88 – 2.77 (m, 2H), 2.58 – 2.50 (m, 2H), 2.00 – 1.90 (m, 4H), 1.83 – 0.99 (m, 26H), 0.91 – 0.89 (m, 6H), 0.87 – 0.85 (m, 6H), 0.66 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 175.5, 146.2, 132.4 (d, JC-P = 96.0 Hz), 131.76 (d, JC-P = 2.6 Hz), 131.11 (d, JC-P = 9.2 Hz), 128.7 (d, JC-P = 11.4 Hz), 128.0, 127.9, 127.1, 122.9, 75.1, 65.51 (d, JC-P = 2.0 Hz), 56.9 (d, JC-P = 20.4), 56.6 (d, JC-P = 73.2 Hz), 50.1, 42.4, 39.9, 39.7, 37.6, 37.0, 36.7, 36.3, 35.9, 32.0 (d, JC-P = 4.9 Hz), 29.6, 28.4, 28.2, 27.3, 24.4, 24.0, 23.0, 22.7, 21.1, 19.4, 18.9, 12.0
³¹P NMR (162 MHz, CDCl₃)	δ 31.0
HRMS (ESI+)	Calculated for C₅₇H₇₃NO₃P [M+H]⁺: 850.5323; found 850.5323

ethyl (S,Z)-6-((5R,8S,9R,10R,13S,14R,17S)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)-3-(diphenylphosphoryl)hept-3-enoate
Identifier	116
¹H NMR (400 MHz, CDCl₃)	δ 7.76 – 7.67 (m, 4H), 7.53 (td, J = 7.5, 3.8 Hz, 2H), 7.49 – 7.37 (m, 4H), 6.4 8 (ddd, J = 20.4, 8.4, 5.9 Hz, 1H), 3.87 (q, J = 7.1 Hz, 2H), 3.33 (dd, J = 14.7, 5.2 Hz, 2H), 2.96 – 2.78 (m, 3H), 2.42 – 2.17 (m, 6H), 2.16 (s, 3H), 2.15 – 1.91 (m, 4H), 1.89 – 1.69 (m, 2H), 1.61 (td, J = 14.2, 5.1 Hz, 1H), 1.49 – 1.40 (m, 1H), 1.39 (s, 3H), 1.35 – 1.20 (m, 2H), 1.10 – 1.00 (m, 5H), 0.82 (d, J = 6.6 Hz, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 211.8, 209.1, 208.8, 169.9 (d, JC-P = 3.0 Hz), 150.4 (d, JC-P = 8.9 Hz), 132.3 (d, JC-P = 9.8 Hz), 132.0 (d, JC-P = 2.8 Hz), 132.0 (d, JC-P = 2.9 Hz), 131.6 (d, JC-P = 102.8 Hz), 131.6 (d, JC-P = 102.8 Hz), 128.6 (d, JC-P = 11.9 Hz), 128.5 (d, JC-P = 12.0 Hz), 127.2 (d, JC-P = 101.2 Hz), 61.0, 57.0, 51.9, 49.1, 46.9, 46.0, 45.7, 45.1, 42.9, 38.7, 36.6 (d, JC-P = 5.4 Hz), 36.1, 36.0, 35.4, 32.9 (d, JC-P = 13.0 Hz), 31.1, 28.0, 25.3, 22.0, 19.7, 14.1, 12.0
³¹P NMR (162 MHz, CDCl₃)	δ 31.5
HRMS (ESI+)	Calculated for C₄₀H₅₀O₆P [M+H]⁺: 657.3340; found 657.3355

methyl 2-(((benzyloxy)carbonyl)amino)-3-(diphenylphosphoryl)propanoate
Identifier	117
¹H NMR (400 MHz, CDCl₃)	δ 7.83 (dd, J = 13.3, 7.2 Hz, 4H), 7.49 – 7.39 (m, 6H), 7.36 – 7.29 (m, 3H), 7.22 – 7.20 (m, 2H), 5.71 (d, J = 7.4 Hz, 1H), 4.86 – 4.71 (m, 1H), 4.82 (d, J = 8.8 Hz, 2H), 3.66 (s, 3H), 3.35 (dt, J = 14.8, 8.7 Hz, 1H), 3.17 (ddd, J = 15.2, 11.2, 4.6 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 171.1, 155.4, 136.1, 131.8 – 131.7 (m, 2C), 131.2 (d, JC-P = 10.5 Hz), 131.0 (d, JC-P = 10.4 Hz), 128.9 (d, JC-P = 13.0 Hz), 128.7 (d, JC-P = 13.0 Hz), 128.6, 128.2, 128.1, 66.9, 52.9, 50.7, 33.1 (d, JC-P = 58.4 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 37.7
HRMS (ESI+)	Calculated for C₂₄H₂₅NO₅P [M+H]⁺: 438.1465; found 438.1471

(E)-(3-((diphenylmethylene)amino)-2,3-diphenylallyl)diphenylphosphine oxide
Identifier	118
¹H NMR (400 MHz, CDCl₃)	δ 7.85 – 7.76 (m, 4H), 7.66 (d, J = 7.7 Hz, 2H), 7.53 – 7.43 (m, 1H), 7.38 (t, J = 7.7 Hz, 4H), 7.33 – 7.23 (m, 4H), 7.23 – 7.08 (m, 4H), 6.96 – 6.85 (m, 5H), 6.84 – 6.78 (m, 2H), 6.73 (t, J = 7.5 Hz, 2H), 6.50 (d, J = 7.6 Hz, 2H), 3.85 (d, J = 15.5 Hz, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.3 (d, JC-P = 3.7 Hz), 147.4 (d, JC-P = 10.5 Hz), 140.2 (d, JC-P = 2.3 Hz), 140.1 (d, JC-P = 2.8 Hz), 139.2, 137.8, 134.1 (d, JC-P = 97.0 Hz), 131.3, 131.3, 130.9, 130.3, 129.5, 129.4 (d, JC-P = 2.7 Hz), 128.6 (d, JC-P = 3.7 Hz), 128.5 (d, JC-P = 3.2 Hz), 128.2, 128.1, 128.0, 127.7, 127.6, 127.0, 126.1 (d, JC-P = 10.3 Hz), 118.8 (d, JC-P = 9.5 Hz), 37.3 (d, JC-P = 68.0 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.06
HRMS (ESI+)	Calculated for C₄₀H₃₆N₂OP [M+NH₄]⁺: 591.2560; found 591.2572

3-(diphenylphosphoryl)-1,2-diphenylpropan-1-one
Identifier	119
¹H NMR (400 MHz, CDCl₃)	δ 7.83 (d, J = 8.0 Hz, 2H), 7.73 – 7.65 (m, 2H), 7.64 – 7.56 (m, 2H), 7.47 – 7.27 (m, 9H), 7.25 – 7.21 (m, 2H), 7.14 – 7.02 (m, 3H), 5.28 (q, J = 6.0 Hz, 1H), 3.47 (ddd, J = 15.2, 10.9, 6.9 Hz, 1H), 2.76 (ddd, J = 15.5, 9.6, 6.1 Hz, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 198.14 (d, JC-P = 6.6 Hz), 138.84, 138.77, 133.29 (d, JC-P = 99.2 Hz), 133.11, 132.29 (d, JC-P = 97.4 Hz), 131.81 (d, JC-P = 2.7 Hz), 131.54 (d, JC-P = 2.8 Hz), 130.97 (d, JC-P = 9.8 Hz), 130.81 (d, JC-P = 9.4 Hz), 129.10, 129.01, 128.59 (d, JC-P = 11.7 Hz), 128.49 (4C), 128.45 (d, JC-P = 11.8 Hz), 127.49, 46.77, 34.04 (d, JC-P = 70.6 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 30.21
HRMS (ESI+)	Calculated for C₂₇H₂₄O₂P [M+H]⁺: 411.1508; found 411.1591

methyl 2-(((benzyloxy)carbonyl)amino)-3-(diphenylphosphaneyl)propanoate
Identifier	120
¹H NMR (400 MHz, CDCl₃)	δ 7.45 – 7.41 (m, 5H), 7.36 – 7.32 (m, 10H), 5.45 (d, J = 8.0 Hz, 1H), 5.05 (s, 2H), 4.59 – 4.51 (m, 1H), 3.53 (s, 3H), 2.72 – 2.67 (m, 1H), 2.55 – 2.50 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.2 (d, JC-P = 5.4 Hz), 155.6, 136.3, 133.1 (d, JC-P = 19.8 Hz), 132.9 (d, JC-P = 19.5 Hz), 129.2 – 129.1 (m, 2C), 128.8 – 128.7 (m, 2C), 128.6, 128.3, 128.2, 67.1,52.4, 52.2 (d, JC-P = 16.1 Hz), 32.2 (d, J = 16.8 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ −24.7
HRMS (ESI+)	Calculated for C₂₄H₂₅NO₄P [M+H]⁺: 422.1516; found 422.1524

2-amino-3-(diphenylphosphoryl)propanoic acid
Identifier	121
¹H NMR (400 MHz, D₂O)	δ 7.63 – 7.47 (m, 6H), 7.43 – 7.35 (m, 4H), 4.27 (dt, J = 13.7, 6.4 Hz, 1H), 3.18 – 3.11 (m, 1H), 3.00 – 2.91 (m, 1H)
¹³C NMR (101 MHz, D₂O)	δ 169.8 (d, JC-P = 8.7 Hz), 133.3 (d, JC-P = 2.9 Hz), 130.6 (d, JC-P = 10.2 Hz), 130.3 (d, JC-P = 10.4 Hz), 129.2 (d, JC-P = 12.4 Hz), 129.2 (d, JC-P = 96.6 Hz), 128.1 (d, JC-P = 96.1 Hz) 48.2 (d, JC-P = 3.6 Hz), 28.5 (d, JC-P = 69.7 Hz)
³¹P NMR (162 MHz, D₂O)	δ 36.7
HRMS (ESI+)	Calculated for C₁₅H₁₆NNaO₃P [M+Na]⁺: 312.0760; found 312.0771

Phospho-DBCO acid
Identifier	122
NMR reporting qualifier	The compound was observed as a mixture of rotamers in CDCl₃ at 298 K. Signals were not distinguishable and are reported together in the ¹H and ¹³C NMR
¹H NMR (400 MHz, CDCl₃)	δ 7.85 – 7.75 (m, 2H), 7.67 – 7.62 (m, 3H), 7.54 – 7.31 (m, 12H), 6.82 – 6.76 (m, 1H), 5.12 (d, J = 13.8 Hz, 1H), 4.62 – 4.50 (m, 1H), 3.63 (d, J = 13.7 Hz, 1H), 3.10 – 2.74 (m, 3H), 2.58 – 2.52 (m, 1H), 2.2. – 2.17 (m, 1H), 1.93 – 1.89 (m, 1H)
¹³C NMR (101 MHz, CDCl₃)	δ 172.0, 172.0, 151.5, 151.5, 148.2, 148.2, 136.4, 134.5, 133.1, 132.9 – 132.3 (m, 4C), 131.7, 131.5 – 131.1 (m, 4C), 130.9 – 130.6 (m, 4C), 129.4 (d, JC-P = 11.9 Hz, 2C), 129.2 – 128.8 (m, 5C), 128.9 – 128.7 (m, 4C), 128.6, 128.5, 128.4 (4C), 128.4 – 128.2 (m, 4C), 127.9 (d, JC-P = 7.7 Hz, 2C), 127.2 (d, JC-P = 7.2 Hz, 2C), 125.7, 125.5, 123.3, 123.2, 122.7, 122.6, 117.7, 115.1, 115.0, 108.1, 107.9, 55.6, 55.6, 48.8, 48.8, 30.6 (d, JC-P = 75.2 Hz), 30.2 (d, JC-P = 79.6 Hz), 30.1, 30.0, 27.8
³¹P NMR (162 MHz, CDCl₃)	δ 34.9, 34.4
HRMS (ESI+)	Calculated for C₃₄H₃₀N₂O₅P [M+H]⁺: 577.1887; found 577.1955

methyl 2-(acetoxy(diphenylphosphoryl)methyl)-3,3-diphenylacrylate
Identifier	124
¹H NMR (400 MHz, CDCl₃)	δ 7.88 (dd, J = 11.4, 7.6 Hz, 2H), 7.65 (dd, J = 11.8, 7.1 Hz, 2H), 7.54 – 7.36 (m, 6H), 7.33 – 7.27 (m, 2H), 7.25 – 7.16 (m, 6H), 7.13 – 7.04 (m, 2H), 6.49 (d, J = 6.6 Hz, 1H), 3.11 (s, 3H), 1.93 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.3 (d, JC-P = 8.4 Hz), 167.9, 152.4 (d, JC-P = 8.7 Hz), 141.1, 139.0, 132.8 (d, JC-P = 9.1 Hz), 132.5 (d, JC-P = 2.5 Hz), 132.4 (d, JC-P = 2.9 Hz), 131.8 (d, JC-P = 9.4 Hz), 131.5 (d, JC-P = 121.0 Hz), 129.6, 128.7 (d, JC-P = 12.0 Hz), 128.6, 128.5 (d, JC-P = 12.7 Hz), 128.5, 128.4, 128.3, 128.3, 128.2, 128.1, 124.2 (d, JC-P = 2.5 Hz), 71.7 (d, JC-P = 87.6 Hz), 51.6, 20.7
³¹P NMR (162 MHz, CDCl₃)	δ 28.1
HRMS (ESI+)	Calculated for C₃₁H₂₈O₅P [M+H]⁺: 511.1669; found 511.1678

methyl 2-(aminodiphenylmethyl)-3-(diphenylphosphoryl)oxirane-2-carboxylate
Identifier	125
¹H NMR (400 MHz, CDCl₃)	δ 7.77 (dd, J = 11.8, 7.6 Hz, 2H), 7.69 (d, J = 7.7 Hz, 2H), 7.60 – 7.51 (m, 2H), 7.50 – 7.37 (m, 6H), 7.23 – 7.04 (m, 8H), 3.71 (d, J = 31.0 Hz, 1H), 3.30 (s, 3H), 2.52 (bs, 2H)
¹³C NMR (101 MHz, CDCl₃)	δ 169.4, 145.2, 144.0, 132.6 (d, JC-P = 3.1 Hz), 132.5 (d, JC-P = 2.9 Hz), 131.6 (d, JC-P = 9.1 Hz), 131.5 (d, JC-P = 106.8 Hz), 131.2 (d, JC-P = 9.8 Hz), 129.0 (d, JC-P = 105.4 Hz), 129.0 (d, JC-P = 12.3 Hz), 128.9 (d, JC-P = 11.8 Hz), 128.7, 127.9, 127.9, 127.3, 127.26, 72.7 (d, JC-P = 2.5 Hz), 64.5, 59.4 (d, JC-P = 92.6 Hz), 52.65
³¹P NMR (162 MHz, CDCl₃)	δ 20.7
HRMS (ESI+)	Calculated for C₂₉H₂₇O₄P [M+H]⁺: 484.1673; found 484.1736

methyl 2-((diphenylphosphoryl)methyl)-3,3-diphenylacrylate
Identifier	126
¹H NMR (400 MHz, CDCl₃)	δ 7.73 (dd, J = 10.9, 7.8 Hz, 4H), 7.57 – 7.38 (m, 6H), 7.28 – 7.16 (m, 8H), 7.09 – 7.04 (m, 2H), 3.56 (d, J = 13.5 Hz, 2H), 3.03 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.27, 150.12 (d, JC-P = 9.9 Hz), 141.93 (d, JC-P = 2.4 Hz), 139.79 (d, JC-P = 2.6 Hz), 132.59 (d, JC-P = 98.7 Hz), 131.99 (d, JC-P = 2.7 Hz), 131.51 (d, JC-P = 9.4 Hz), 129.63, 129.61, 128.59 (d, JC-P = 11.6 Hz), 128.57 (d, JC-P = 2.5 Hz), 128.36, 128.17, 128.02, 127.79, 123.09 (d, JC-P = 8.7 Hz), 51.56, 34.95 (d, JC-P = 68.5 Hz)
³¹P NMR (162 MHz, CDCl₃)	δ 27.7
HRMS (ESI+)	Calculated for C₂₉H₂₆O₃P [M+H]⁺: 453.1615; found 453.1615

methyl (E)-2-(diphenylmethylene)-4-phenylbut-3-enoate
Identifier	127
¹H NMR (400 MHz, CDCl₃)	δ 7.38 (d, J = 6.5 Hz, 3H), 7.34 – 7.17 (m, 12H), 6.91 (d, J = 16.4 Hz, 1H), 6.64 (d, J = 16.4 Hz, 1H), 3.61 (s, 3H)
¹³C NMR (101 MHz, CDCl₃)	δ 170.5, 145.0, 141.9, 140.1, 137.2, 132.5, 132.4, 131.0, 129.2, 128.7, 128.4, 128.3, 128.3, 128.2, 128.0, 126.8, 125.1, 52.1
³¹P NMR (162 MHz, CDCl₃)	δ 27.7
HRMS (ESI+)	Calculated for C₂₄H₂₁O₂ [M+H]⁺: 341.1536; found 341.1550

Reaction of 59 with methyl acrylate 61 in CD₂Cl₂ without added water
¹H and ³¹P NMR monitoring, sample	Methyl acrylate 61 (4.5 µL, 0.050 mmol, 1.0 equiv), 1,3,5-trimethoxybenzene (8.4 mg, 0.050 mmol, 1.0 equiv) as an internal standard, and iminyl phosphine 59 (20.1 mg, 0.055 mmol, 1.1 equiv) in CD₂Cl₂ (0.5 mL)
¹H and ³¹P NMR monitoring, time points	30 min and 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, and 28 h; after addition of excess water, an additional 30 min
¹H and ³¹P NMR monitoring, observations	Product 29 was detected after 30 min; cyclic intermediate 62 became evident after 1 h; the reaction rate decreased markedly after approximately 6 h; methyl acrylate 61 was completely consumed after 28 h; after water was added and the mixture was stirred for an additional 30 min, cyclic intermediate 62 disappeared concomitant with an increase in product 29
³¹P NMR kinetic analysis	Cyclic intermediate 62 was detected at δ 49.5, while only low conversion of 61 was observed; upon addition of H₂O, intermediate 62 was rapidly converted into 29 within 5 min
³¹P NMR spectrum annotations	δ 30.6, 37.7, 49.5

Reaction of 59 with methyl acrylate 61 in CD₂Cl₂ with excess H₂O
¹H and ³¹P NMR monitoring, sample	Methyl acrylate 61 (4.5 µL, 0.050 mmol, 1.0 equiv), 1,3,5-trimethoxybenzene (8.4 mg, 0.050 mmol, 1.0 equiv) as an internal standard, iminyl phosphine 59 (20.1 mg, 0.055 mmol, 1.1 equiv) in CD₂Cl₂ (0.5 mL), and H₂O (0.1 mL)
¹H and ³¹P NMR monitoring, time points	30 min and 1, 2, 4, 6, 8, 10, and 12 h
¹H and ³¹P NMR monitoring, observations	Cyclic intermediate 62 was not detected; methyl acrylate 61 was initially consumed at a rate comparable to that without added water; after approximately 6 h, a clear change in the reaction rate was observed; methyl acrylate 61 was completely consumed within 12 h
³¹P NMR spectrum annotations	δ 17.7, 31.7, 37.7

Alkene-derived reaction in DCE
³¹P NMR	δ 42.7, unassigned

C₂₈H₂₅N₂OP
Identifier	CCDC 2574019
Empirical formula	C₂₈H₂₅N₂OP
Formula weight	436.17
Temperature [K]	170.00
Crystal system	monoclinic
Space group (number)	P2₁/c (14)
a [Å]	5.9088(2)
b [Å]	20.4123(6)
c [Å]	20.3511(6)
α [°]	90
β [°]	93.9580(10)
γ [°]	90
Volume [Å³]	2448.74(13)
Z	4.0
ρcalc [g cm⁻³]	1.188
μ [mm⁻¹]	1.185
F(000)	923
Crystal size [mm³]	0.02×0.08×0.66
Crystal colour	translucent colourless
Crystal shape	plate
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	6.14 to 150.28 (0.80 Å)
Index ranges	−7 ≤ h ≤ 7; −25 ≤ k ≤ 25; −25 ≤ l ≤ 21
Reflections collected	66917
Independent reflections	5004; Rint = 0.0549; Rsigma = 0.0252
Completeness to θ = 67.679°	99.7
Data / Restraints / Parameters	5004 / 0 / 295
Goodness-of-fit on F²	1.108
Final R indexes [I≥2σ(I)]	R1 = 0.0418; wR2 = 0.1077
Final R indexes [all data]	R1 = 0.0435; wR2 = 0.1089
Largest peak/hole [e Å⁻³]	0.39/−0.30

C₂₉H₂₆NO₃P
Identifier	CCDC 2570258
Empirical formula	C₂₉H₂₆NO₃P
Formula weight	467.17
Temperature [K]	298.00
Crystal system	triclinic
Space group (number)	P1 (2)
a [Å]	11.5873(2)
b [Å]	11.6236(2)
c [Å]	13.4081(2)
α [°]	95.8190(10)
β [°]	106.3050(10)
γ [°]	117.3990(10)
Volume [Å³]	1481.41(4)
Z	4.0
ρcalc [g cm⁻³]	1.238
μ [mm⁻¹]	2.722
F(000)	576
Crystal size [mm³]	0.03×0.075×0.16
Crystal colour	translucent colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	7.14 to 161.35 (0.78 Å)
Index ranges	−14 ≤ h ≤ 14; −14 ≤ k ≤ 14; −17 ≤ l ≤ 16
Reflections collected	39755
Independent reflections	6355; Rint = 0.0544; Rsigma = 0.0334
Completeness to θ = 67.679°	100.0
Data / Restraints / Parameters	6355 / 1 / 342
Goodness-of-fit on F²	1.063
Final R indexes [I≥2σ(I)]	R1 = 0.0587; wR2 = 0.1576
Final R indexes [all data]	R1 = 0.0677; wR2 = 0.1652
Largest peak/hole [e Å⁻³]	1.28/−0.39
Extinction coefficient	0.0076(6)

C₄₂H₃₇N₂O₂P
Identifier	CCDC 2570255
Empirical formula	C₄₂H₃₇N₂O₂P
Formula weight	632.25
Temperature [K]	298.00
Crystal system	monoclinic
Space group (number)	P2₁/c (14)
a [Å]	11.2616(2)
b [Å]	12.4857(2)
c [Å]	24.3982(4)
α [°]	90
β [°]	94.0600(10)
γ [°]	90
Volume [Å³]	3422.00(10)
Z	4.0
ρcalc [g cm⁻³]	1.228
μ [mm⁻¹]	1.009
F(000)	1336
Crystal size [mm³]	0.06×0.085×0.155
Crystal colour	translucent light colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	7.26 to 160.08 (0.78 Å)
Index ranges	−14 ≤ h ≤ 14; −14 ≤ k ≤ 15; −30 ≤ l ≤ 31
Reflections collected	49222
Independent reflections	7305; Rint = 0.0706; Rsigma = 0.0385
Completeness to θ = 67.679°	100.0
Data / Restraints / Parameters	7305 / 12 / 409
Goodness-of-fit on F²	1.036
Final R indexes [I≥2σ(I)]	R1 = 0.0509; wR2 = 0.1285
Final R indexes [all data]	R1 = 0.0671; wR2 = 0.1408
Largest peak/hole [e Å⁻³]	0.58/−0.51

C₃₃H₃₁NO₂P
Identifier	CCDC 2574020
Empirical formula	C₃₃H₃₁NO₂P
Formula weight	504.20
Temperature [K]	298.00
Crystal system	triclinic
Space group (number)	P1 (2)
a [Å]	7.8477(9)
b [Å]	14.2873(17)
c [Å]	15.6090(17)
α [°]	90.467(6)
β [°]	98.156(5)
γ [°]	100.143(6)
Volume [Å³]	1704.4(3)
Z	2.0
ρcalc [g cm⁻³]	1.312
μ [mm⁻¹]	3.848
F(000)	700
Crystal size [mm³]	0.055×0.08×0.155
Crystal colour	translucent colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	11.46 to 163.55 (0.78 Å)
Index ranges	−8 ≤ h ≤ 9; −18 ≤ k ≤ 18; −19 ≤ l ≤ 19
Reflections collected	30871
Independent reflections	7131; Rint = 0.0636; Rsigma = 0.0471
Completeness to θ = 67.679°	99.3
Data / Restraints / Parameters	7131 / 47 / 388
Goodness-of-fit on F²	1.048
Final R indexes [I≥2σ(I)]	R1 = 0.0682; wR2 = 0.1918
Final R indexes [all data]	R1 = 0.0798; wR2 = 0.2036
Largest peak/hole [e Å⁻³]	0.66/−0.68

C₃₃H₃₂NO₂P
Identifier	CCDC 2574021
Empirical formula	C₃₃H₃₂NO₂P
Formula weight	502.21
Temperature [K]	298.00
Crystal system	triclinic
Space group (number)	P1 (2)
a [Å]	8.6055(2)
b [Å]	10.6197(2)
c [Å]	18.8513(4)
α [°]	98.1020(10)
β [°]	90.3000(10)
γ [°]	110.8940(10)
Volume [Å³]	1590.56(6)
Z	2.0
ρcalc [g cm⁻³]	1.144
μ [mm⁻¹]	1.752
F(000)	578
Crystal size [mm³]	0.03×0.12×0.125
Crystal colour	translucent colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	4.74 to 162.72 (0.78 Å)
Index ranges	−10 ≤ h ≤ 10; −13 ≤ k ≤ 13; −23 ≤ l ≤ 24
Reflections collected	63848
Independent reflections	6861; Rint = 0.0532; Rsigma = 0.0284
Completeness to θ = 67.679°	99.8
Data / Restraints / Parameters	6861 / 72 / 337
Goodness-of-fit on F²	1.029
Final R indexes [I≥2σ(I)]	R1 = 0.0473; wR2 = 0.1319
Final R indexes [all data]	R1 = 0.0526; wR2 = 0.1367
Largest peak/hole [e Å⁻³]	0.59/−0.34

C₂₃H₂₂NO₃P
Identifier	CCDC 2570257
Empirical formula	C₂₃H₂₂NO₃P
Formula weight	391.13
Temperature [K]	298.00
Crystal system	monoclinic
Space group (number)	P2₁/n (14)
a [Å]	10.8862(2)
b [Å]	9.88180(10)
c [Å]	19.2874(3)
α [°]	90
β [°]	92.6320(10)
γ [°]	90
Volume [Å³]	2072.66(5)
Z	2.0
ρcalc [g cm⁻³]	1.254
μ [mm⁻¹]	1.360
F(000)	824
Crystal size [mm³]	0.06×0.07×0.14
Crystal colour	translucent colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	9.18 to 160.24 (0.78 Å)
Index ranges	−13 ≤ h ≤ 13; −12 ≤ k ≤ 12; −24 ≤ l ≤ 24
Reflections collected	43766
Independent reflections	4453; Rint = 0.0645; Rsigma = 0.0298
Completeness to θ = 67.679°	100.0
Data / Restraints / Parameters	4453 / 0 / 255
Goodness-of-fit on F²	1.062
Final R indexes [I≥2σ(I)]	R1 = 0.0406; wR2 = 0.1113
Final R indexes [all data]	R1 = 0.0469; wR2 = 0.1167
Largest peak/hole [e Å⁻³]	0.43/−0.44

C₃₆H₃₀NO₃P
Identifier	CCDC 2570256
Empirical formula	C₃₆H₃₀NO₃P
Formula weight	555.19
Temperature [K]	298.00
Crystal system	monoclinic
Space group (number)	C2/c (15)
a [Å]	23.8287(6)
b [Å]	8.6564(3)
c [Å]	29.1864(8)
α [°]	90
β [°]	95.558(2)
γ [°]	90
Volume [Å³]	5992.0(3)
Z	12.0
ρcalc [g cm⁻³]	1.229
μ [mm⁻¹]	1.098
F(000)	2328
Crystal size [mm³]	0.025×0.03×0.115
Crystal colour	translucent colourless
Crystal shape	Fragment (Prism)
Radiation	CuKα (λ=1.54178 Å)
2θ range [°]	6.08 to 161.55 (0.78 Å)
Index ranges	−28 ≤ h ≤ 30; −10 ≤ k ≤ 10; −37 ≤ l ≤ 37
Reflections collected	72597
Independent reflections	6468; Rint = 0.1112; Rsigma = 0.0658
Completeness to θ = 67.679°	99.9
Data / Restraints / Parameters	6468 / 0 / 372
Goodness-of-fit on F²	1.036
Final R indexes [I≥2σ(I)]	R1 = 0.0521; wR2 = 0.1342
Final R indexes [all data]	R1 = 0.0721; wR2 = 0.1500
Largest peak/hole [e Å⁻³]	0.59/−0.19
Extinction coefficient	0.00088(11)