Joshua O. Imasuen, Baiyang Jiang, Manolis Sofiadis, Kaid C. Harper, Daiki Yamamoto, Tomoya Imai, Alexandros S. Pollatos, Philipp Neigenfind, Yu Kawamata, Phil S. Baran. “Simultaneous two-directional catalytic radical cross-coupling.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007839/v1

22
¹H NMR (600 MHz, CDCl₃) δ 9.98 (s, 1H), 7.62–7.53 (m, 3H), 7.53–7.41 (m, 4H), 7.27–7.19 (m, 3H), 6.78–6.69 (m, 3H), 4.38 (dd, J = 5.8, 3.2 Hz, 3H), 4.32 (dd, J = 5.5, 3.2 Hz, 3H); image caption specifies 400 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 192.2, 159.3, 158.6, 138.5, 138.0, 130.3, 124.3, 122.4, 117.2, 112.8, 83.5, 66.6; image data were not transcribed
HRMS (ESI+) Calculated for C₁₅H₁₄IO₃ [M+H]⁺: 368.9988, found: 368.9980
TLC Rf (hexanes/CH₂Cl₂/Et₂O 5/1/1, UV) 0.42
SI, pp. 6, 60–61
21
¹H NMR (600 MHz, CDCl₃) δ 7.94–7.87 (m, 4H), 7.84–7.77 (m, 4H), 4.64 (s, 2H), 4.46 (s, 2H), 1.53 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 166.5, 166.3, 161.6, 161.5, 154.3, 135.1, 135.0, 128.9, 124.3, 83.2, 47.6, 47.1, 28.1; image data were not transcribed
HRMS (ESI+) Calculated for C₂₀H₁₄N₃O₈ [M−Boc+2H]⁺: 424.0781, found: 424.0773
SI, pp. 11, 62–63
S1
¹H NMR (600 MHz, CDCl₃) δ 7.89 (dd, J = 5.4, 3.1 Hz, 4H), 7.80 (dd, 4H), 3.19 (s, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 167.8, 161.7, 135.0, 129.0, 124.2, 26.1; image data were not transcribed
HRMS (ESI+) Calculated for C₂₀H₁₃N₂O₈ [M+H]⁺: 409.0672, found: 409.0676
SI, pp. 12, 64–65
S2
¹H NMR (400 MHz, CDCl₃) δ 7.95–7.85 (m, 4H), 7.85–7.75 (m, 4H), 2.90 (t, J = 7.3 Hz, 4H), 2.28 (p, J = 7.3 Hz, 2H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 168.9, 162.0, 135.0, 129.0, 124.2, 29.8, 19.9; image data were not transcribed
HRMS (ESI+) Calculated for C₂₁H₁₅N₂O₈ [M+H]⁺: 423.0828, found: 423.0829
SI, pp. 13, 66–67
S3
¹H NMR (400 MHz, CDCl₃) δ 7.94–7.84 (m, 4H), 7.84–7.75 (m, 4H), 2.78–2.74 (m, 4H), 2.03–1.91 (m, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 169.2, 162.1, 134.9, 129.1, 124.1, 30.7, 23.9; image data were not transcribed
HRMS (ESI+) Calculated for C₂₂H₁₇N₂O₈ [M+H]⁺: 437.0985, found: 437.0996
SI, pp. 14, 68–69
S4
¹H NMR (400 MHz, CDCl₃) δ 7.96–7.87 (m, 4H), 7.87–7.77 (m, 4H), 4.75 (s, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 166.0, 161.6, 135.1, 128.9, 124.3, 66.4; image data were not transcribed
HRMS (ESI+) Calculated for C₂₀H₁₃N₂O₉ [M+H]⁺: 425.0621, found: 425.0633
SI, pp. 15, 70–71
S5
¹H NMR (600 MHz, CDCl₃) δ 7.92–7.86 (m, 4H), 7.82–7.76 (m, 4H), 3.92 (t, J = 6.4 Hz, 4H), 3.00 (t, J = 6.4 Hz, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 167.7, 161.8, 134.8, 128.9, 124.0, 65.8, 32.1; image data were not transcribed
HRMS (ESI+) Calculated for C₂₂H₁₇N₂O₉ [M+H]⁺: 453.0934, found: 453.0929
SI, pp. 16, 72–73
S6
¹H NMR (600 MHz, CDCl₃) δ 7.88 (dd, J = 5.5, 3.1 Hz, 4H), 7.78 (dd, J = 5.5, 3.1 Hz, 4H), 3.71 (t, J = 6.8 Hz, 4H), 3.10–2.81 (m, 4H), 1.51 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 168.6, 168.1, 161.9, 155.0, 134.9, 129.0, 124.2, 81.1, 44.9, 44.8, 31.3, 30.7, 28.5; image data were not transcribed
HRMS (ESI+) Calculated for C₂₂H₁₈N₃O₈ [M−Boc+2H]⁺: 452.1094, found: 452.1105
SI, pp. 17, 74–75
S7
¹H NMR (600 MHz, CDCl₃) δ 7.92–7.85 (m, 4H), 7.82–7.76 (m, 4H), 3.88 (s, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 166.1, 161.7, 135.1, 128.9, 124.2, 30.0; image data were not transcribed
HRMS (ESI+) Calculated for C₂₀H₁₃N₂O₈S [M+H]⁺: 441.0393, found: 441.0403
SI, pp. 18, 76–77
S8
¹H NMR (600 MHz, CDCl₃) δ 7.90 (dd, J = 5.5, 3.1 Hz, 4H), 7.84–7.78 (m, 4H), 5.67 (s, 2H), 3.42–3.32 (m, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 170.9, 165.0, 161.5, 135.2, 128.8, 95.7, 75.2, 38.6; image data were not transcribed
HRMS (ESI+) Calculated for C₂₃H₁₅N₂O₁₁ [M+H]⁺: 495.0676, found: 495.0690
SI, pp. 19, 78–79
33
¹H NMR (400 MHz, CDCl₃) δ 10.01 (s, 2H), 7.85 (d, J = 8.1 Hz, 4H), 7.36 (d, J = 16.7 Hz, 4H), 4.61–4.25 (m, 4H), 1.48 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 191.8, 155.8, 144.9, 144.7, 135.7, 130.1, 128.3, 127.6, 81.0, 77.1, 50.1, 49.8, 28.4; image data were not transcribed
HRMS (ESI+) Calculated for C₁₆H₁₆NO₂ [M−Boc+2H]⁺: 254.1181, found: 254.1178
TLC Rf (hexanes/EtOAc 7/3, UV) 0.43
SI, pp. 20, 80–81
34
¹H NMR (600 MHz, CDCl₃) δ 7.77 (d, J = 8.0 Hz, 4H), 7.25–7.15 (m, 4H), 4.76–3.92 (m, 4H), 1.47 (s, 9H), 1.35 (s, 24H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 156.2, 141.3, 141.2, 135.2, 127.5, 126.7, 83.9, 80.3, 49.5, 49.3, 28.5, 25.0; image data were not transcribed
HRMS (ESI+) Not detected
TLC Rf (hexanes/EtOAc 9/1, UV) 0.40
SI, pp. 21, 82–83
35
¹H NMR (600 MHz, CDCl₃) δ 7.32–7.27 (m, 4H), 7.19–7.07 (m, 4H), 4.32 (d, 4H), 1.48 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.9, 136.4, 133.3, 129.5, 128.9, 80.7, 49.0, 48.7, 28.5; image data were not transcribed
HRMS (ESI+) Calculated for C₁₄H₁₄Cl₂N [M−Boc+2H]⁺: 266.0503, found: 266.0503
TLC Rf (hexanes/EtOAc 9/1, UV) 0.40
SI, pp. 22, 84–85
36
¹H NMR (400 MHz, CDCl₃) δ 7.20–7.06 (m, 4H), 6.90–6.82 (m, 4H), 4.28 (d, 4H), 3.81 (s, 6H), 1.50 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 191.8, 155.8, 144.9, 144.7, 135.7, 130.1, 128.3, 127.6, 81.0, 77.1, 50.1, 49.8, 28.4; image data were not transcribed
HRMS (ESI+) Calculated for C₂₁H₂₇NO₄Na [M+Na]⁺: 380.1838, found: 380.1832
TLC Rf (hexanes/EtOAc 9/1, UV) 0.21
SI, pp. 23, 86–87
38
¹H NMR (400 MHz, CDCl₃) δ 7.20–7.03 (m, 4H), 6.90–6.85 (m, 4H), 4.52–4.16 (m, 4H), 3.89–3.84 (m, 8H), 3.17–3.13 (m, 8H), 1.50 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 156.1, 150.6, 129.6, 129.3, 128.7, 115.8, 79.9, 67.0, 49.5, 48.3, 48.0, 28.6; image data were not transcribed
HRMS (ESI+) Calculated for C₂₇H₃₇N₃O₄Na [M+Na]⁺: 490.2682, found: 490.2693
TLC Rf (hexanes/EtOAc 7/3, UV) 0.25
SI, pp. 24, 88–89
37
¹H NMR (600 MHz, CDCl₃) δ 7.58 (d, J = 8.0 Hz, 4H), 7.34–7.27 (m, 4H), 4.54–4.38 (m, 4H), 1.49 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.9, 142.0 (d, J = 19.7 Hz), 129.9 (q, J = 32.4 Hz), 127.9 (d, J = 97.5 Hz), 125.7 (q, J = 3.8 Hz), 125.1, 123.3, 81.0, 49.5 (d, J = 51.3 Hz), 28.5; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −62.52; image data were not transcribed
HRMS (ESI+) Calculated for C₁₆H₁₄F₆N [M−Boc+2H]⁺: 334.1030, found: 334.1041
TLC Rf (hexanes/EtOAc 9/1, UV) 0.37
SI, pp. 25, 90–92
24
¹H NMR (400 MHz, CDCl₃) δ 8.23 (d, J = 2.5 Hz, 2H), 7.64–7.39 (m, 2H), 7.30 (d, J = 8.2 Hz, 2H), 4.37 (s, 4H), 1.48 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.5, 151.0, 149.1, 138.8, 138.0, 132.2, 124.5, 81.6, 47.2, 47.0, 28.5; image data were not transcribed
HRMS (ESI+) Calculated for C₁₇H₂₀Cl₂N₃O₂ [M+H]⁺: 368.0933, found: 368.0929
TLC Rf (hexanes/acetone 7/3, UV) 0.48
SI, pp. 26, 93–94
25
¹H NMR (600 MHz, CDCl₃) δ 7.8 (d, J = 1.8 Hz, 2H), 7.6–7.4 (m, 2H), 4.4 (s, 4H), 1.5 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.4, 152.6 (d, J = 14.6 Hz), 151.0 (d, J = 14.6 Hz), 146.6 (d, J = 28.4 Hz), 144.8 (d, J = 28.1 Hz), 140.4, 132.9 (d, J = 5.0 Hz), 126.2 (d, J = 115.9 Hz), 82.1, 46.7, 28.5; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −87.88 (d, J = 27.3 Hz), −138.58 (d, J = 26.8 Hz); image data were not transcribed
HRMS (ESI+) Calculated for C₁₇H₁₈N₃F₄O₂ [M+H]⁺: 372.1335, found: 372.1349
TLC Rf (hexanes/EtOAc 85/15, UV) 0.18
SI, pp. 27, 95–97
27
¹H NMR (600 MHz, CDCl₃) δ 8.18 (d, J = 5.2 Hz, 2H), 7.07–6.96 (m, 2H), 6.82–6.70 (m, 2H), 4.57–4.29 (m, 4H), 1.46 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 165.2, 163.6, 155.5, 152.8 (d, J = 49.6 Hz), 148.3 (d, J = 15.0 Hz), 119.9 (d, J = 93.6 Hz), 107.8 (dd, J = 81.8, 37.6 Hz), 81.9, 49.5 (d, J = 50.2 Hz), 28.4; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −67.39 (d, J = 30.0 Hz); image data were not transcribed
HRMS (ESI+) Calculated for C₁₇H₂₀F₂N₃O₂ [M+H]⁺: 336.1524, found: 336.1515
TLC Rf (hexanes/EtOAc 6/4, UV) 0.35
SI, pp. 28, 98–100
28
¹H NMR (400 MHz, CDCl₃) δ 8.68 (d, J = 5.0 Hz, 2H), 7.54 (s, 2H), 7.35 (s, 2H), 4.74–4.23 (m, 4H), 1.45 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.3, 151.6, 148.5 (d, J = 40.4 Hz), 134.6 (d, J = 4.0 Hz), 126.8 (d, J = 71.0 Hz), 125.2 (d, J = 113.0 Hz), 117.1, 82.6, 49.6 (d, J = 37.9 Hz), 28.3; image data were not transcribed
HRMS (ESI+) Calculated for C₁₉H₂₀N₅O₂ [M+H]⁺: 350.1617, found: 350.1617
TLC Rf (hexanes/EtOAc 8/1, UV) 0.25
SI, pp. 29, 101–102
29
¹H NMR (600 MHz, CDCl₃) δ 7.51 (t, J = 7.7 Hz, 2H), 6.84 (d, J = 7.2 Hz, 1H), 6.75 (d, J = 7.3 Hz, 1H), 6.59 (d, J = 8.3 Hz, 2H), 4.88–4.28 (m, 4H), 3.88 (d, J = 3.6 Hz, 6H), 1.41 (s, 9H); image caption specifies 400 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 163.8, 156.4, 156.2, 155.9, 139.1, 139.0, 114.1, 113.5, 108.9, 108.8, 80.0, 53.4, 52.7, 52.3, 28.5; image data were not transcribed
HRMS (ESI+) Calculated for C₁₉H₂₆N₃O₄ [M+H]⁺: 360.1923, found: 360.1925
TLC Rf (hexanes/EtOAc 8/2, UV) 0.50
SI, pp. 30, 103–104
30
¹H NMR (400 MHz, CDCl₃) δ 9.17 (s, 2H), 8.65 (s, 4H), 4.42 (s, 4H), 1.49 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 158.4, 156.5, 155.3, 131.1, 82.2, 46.1, 28.4; image data were not transcribed
HRMS (ESI+) Not detected
TLC Rf (CH₂Cl₂/iPrOH/acetic acid 95.5/4/0.5, UV) 0.32
SI, pp. 31, 105–106
26
¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 2H), 8.10 (dd, J = 8.4, 1.1 Hz, 2H), 8.05–7.85 (m, 2H), 7.77 (d, J = 8.0 Hz, 2H), 7.71 (ddd, J = 8.4, 6.8, 1.4 Hz, 2H), 7.59–7.53 (m, 2H), 5.27–4.25 (m, 4H), 1.54 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.9, 151.0, 150.6, 147.8, 135.0, 134.3, 130.5, 129.6, 129.5, 127.9, 127.7, 127.2, 81.3, 47.9, 47.6, 28.6; image data were not transcribed
HRMS (ESI+) Calculated for C₂₅H₂₆N₃O₂ [M+H]⁺: 400.2025, found: 400.2021
TLC Rf (hexanes/EtOAc 4/6, UV) 0.21
SI, pp. 32, 107–108
31
¹H NMR (400 MHz, CDCl₃) δ 7.54 (d, J = 3.8 Hz, 2H), 7.05–6.83 (m, 2H), 4.78–4.42 (m, 4H), 2.53 (s, 6H), 1.52 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 190.7, 154.7, 149.9, 144.2, 144.1, 132.7, 132.5, 127.4, 127.1, 81.7, 45.4, 44.9, 28.5, 26.8; image data were not transcribed
HRMS (ESI+) Calculated for C₁₉H₂₃NO₄ [M+Na]⁺: 416.0966, found: 416.0979
TLC Rf (CH₂Cl₂/EtOAc 8/1, UV) 0.50
SI, pp. 33, 109–110
32
¹H NMR (600 MHz, MeOD) δ 7.16–7.10 (m, 4H), 7.10–6.97 (m, 4H), 4.35–4.15 (m, 6H), 3.07 (dd, J = 13.9, 5.0 Hz, 2H), 2.81 (dd, J = 13.8, 9.1 Hz, 2H), 1.38 (s, 9H), 1.29 (s, 18H); image data were not transcribed
¹³C NMR (151 MHz, MeOD) δ 174.0, 156.4, 156.3, 136.5, 136.3, 136.0, 129.2, 127.5, 127.2, 80.3, 79.1, 54.9, 49.0, 48.6, 37.0, 27.3; image data were not transcribed
HRMS (ESI+) Calculated for C₁₉H₂₀F₆N₃O₃ [M+H]⁺: 436.1460, found: 436.1459
SI, pp. 34, 111–112
40
¹H NMR (400 MHz, CDCl₃) δ 8.59 (s, 2H), 7.80–7.60 (m, 4H), 4.50 (s, 4H), 1.49 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 155.5, 149.4, 147.8 (q, J = 34.9 Hz), 137.9–136.2 (m), 124.3, 122.4, 120.6, 118.8, 82.0, 47.8 (d, J = 53.4 Hz), 28.4; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −67.91; image data were not transcribed
HRMS (ESI+) Calculated for C₁₉H₂₀F₆N₃O₃ [M+H]⁺: 436.1460, found: 436.1459
TLC Rf (CH₂Cl₂/EtOAc 95/5, UV) 0.40
SI, pp. 35, 113–115
41
¹H NMR (400 MHz, CDCl₃) δ 8.56 (dd, J = 5.0, 0.8 Hz, 2H), 7.69 (dd, J = 1.8, 0.9 Hz, 2H), 7.42 (dd, J = 5.1, 1.7 Hz, 2H), 3.02 (s, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 152.5, 152.0, 134.4, 130.0, 128.6, 35.2; image data were not transcribed
HRMS (ESI+) Calculated for C₁₄H₁₁N₄ [M+H]⁺: 235.0984, found: 235.0979
TLC Rf (hexanes/EtOAc 4/6, UV) 0.27
SI, pp. 36, 116–117
42
¹H NMR (600 MHz, CDCl₃) δ 8.62 (d, J = 5.0 Hz, 2H), 7.54 (s, 2H), 7.34 (dd, J = 5.1, 1.7 Hz, 2H), 2.75 (t, J = 7.9 Hz, 4H), 2.07–1.98 (m, 2H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 151.7, 151.3, 134.3, 128.6, 127.0, 117.3, 34.3, 30.2; image data were not transcribed
HRMS (ESI+) Calculated for C₁₅H₁₃N₄ [M+H]⁺: 249.1140, found: 249.1136
TLC Rf (hexanes/EtOAc 1/1, UV) 0.20
SI, pp. 37, 118–119
43
¹H NMR (600 MHz, CDCl₃) δ 8.59 (d, J = 5.0 Hz, 2H), 7.51 (d, J = 1.7 Hz, 2H), 7.32 (dd, J = 5.2, 1.7 Hz, 2H), 2.76–2.67 (m, 4H), 1.75–1.67 (m, J = 4.8, 4.3 Hz, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 152.4, 151.2, 134.2, 128.7, 127.1, 117.4, 34.8, 29.6; image data were not transcribed
HRMS (ESI+) Calculated for C₁₆H₁₅N₄ [M+H]⁺: 263.1297, found: 263.1299
TLC Rf (hexanes/CH₂Cl₂/EtOAc 4/1/1, UV) 0.23
SI, pp. 38, 120–121
45
¹H NMR (400 MHz, CDCl₃) δ 8.17 (dd, J = 5.0, 0.8 Hz, 2H), 7.50 (dd, J = 1.7, 0.9 Hz, 2H), 7.20 (dd, J = 5.2, 1.6 Hz, 2H), 4.18 (s, 4H); image caption specifies 600 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 113.1, 111.3, 94.5, 88.7, 87.4, 79.4, 31.4; image data were not transcribed
HRMS (ESI+) Calculated for C₁₄H₁₁N₄O [M+H]⁺: 251.0933, found: 251.0937
TLC Rf (hexanes/EtOAc 4/6, UV) 0.27
SI, pp. 39, 122–123
48
¹H NMR (600 MHz, CDCl₃) δ 8.58 (dd, J = 5.0, 0.8 Hz, 2H), 7.53 (d, J = 1.7 Hz, 2H), 7.31 (dd, J = 5.1, 1.7 Hz, 2H), 3.68 (t, J = 6.1 Hz, 4H), 2.90 (t, J = 6.1 Hz, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 151.0, 150.1, 134.0, 129.2, 127.6, 117.4, 69.9, 35.3; image data were not transcribed
HRMS (ESI+) Calculated for C₁₆H₁₅N₄O [M+H]⁺: 279.1246, found: 279.1248
TLC Rf (hexanes/EtOAc 3/7, UV) 0.41
SI, pp. 40, 124–125
47
¹H NMR (400 MHz, CDCl₃) δ 8.61 (d, J = 5.0 Hz, 2H), 7.53 (d, J = 9.0 Hz, 2H), 7.41–7.27 (m, 2H), 3.48–3.34 (m, 4H), 2.94–2.80 (m, 4H), 1.37 (s, 9H); image caption specifies 600 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 154.9, 151.3, 149.7, 129.1, 127.6, 117.3, 80.9, 48.2, 47.8, 34.4, 33.7, 28.4; image data were not transcribed
HRMS (ESI+) Calculated for C₂₁H₂₄N₅O₂ [M+H]⁺: 378.1930, found: 378.1928
TLC Rf (hexanes/EtOAc 4/6, UV) 0.24
SI, pp. 41, 126–127
46
¹H NMR (600 MHz, CDCl₃) δ 8.67 (d, J = 5.0 Hz, 2H), 7.66 (d, J = 1.8 Hz, 2H), 7.41 (dd, J = 5.0, 1.8 Hz, 2H), 3.63 (s, 4H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 151.5, 148.2, 134.6, 128.6, 127.1, 117.0, 34.6; image data were not transcribed
HRMS (ESI+) Calculated for C₁₄H₁₁N₄S [M+H]⁺: 267.0704, found: 267.0705
TLC Rf (hexanes/EtOAc 1/1, UV) 0.23
SI, pp. 42, 128–129
44
¹H NMR (400 MHz, CDCl₃) δ 8.68 (dd, J = 5.0, 0.9 Hz, 2H), 7.62 (dd, J = 1.7, 0.8 Hz, 2H), 7.42 (dd, J = 5.0, 1.7 Hz, 2H), 4.92 (s, 2H), 3.24 (d, J = 13.9 Hz, 2H), 3.11 (d, J = 13.9 Hz, 2H); image caption specifies 600 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 171.4, 151.6, 144.4, 134.6, 130.2, 128.8, 117.0, 94.4, 81.3, 41.4; image data were not transcribed
HRMS (ESI+) Calculated for C₁₇H₁₃N₄O₃ [M+H]⁺: 321.0988, found: 321.0995
TLC Rf (hexanes/EtOAc 4/6, UV) 0.30
SI, pp. 43, 130–131
18
¹H NMR (600 MHz, CDCl₃) δ 9.99 (d, J = 1.8 Hz, 2H), 7.52–7.44 (m, 6H), 7.28–7.22 (m, 2H), 7.19–7.11 (m, 4H), 6.91 (dd, J = 8.3, 2.0 Hz, 4H), 4.54–4.17 (m, 12H), 1.50 (d, J = 1.9 Hz, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 192.2, 159.4, 157.9, 156.1, 137.9, 130.8, 130.3, 129.6, 129.0, 122.4, 114.8, 112.8, 80.1, 66.9, 66.6, 48.5, 48.2, 28.6; image data were not transcribed
HRMS (ESI+) Calculated for C₃₂H₃₂NO₆ [M+H]⁺: 526.2230, found: 526.2223
TLC Rf (hexanes/EtOAc/CH₂Cl₂ 7/3/0.5, UV) 0.28
SI, pp. 44, 132–133
S9
¹H NMR (600 MHz, CDCl₃) δ 7.74 (d, J = 8.3 Hz, 4H), 7.37–7.28 (m, 4H), 4.81 (s, 2H), 2.88 (t, J = 7.1 Hz, 4H), 2.41 (s, 6H), 1.40 (p, J = 7.1 Hz, 4H), 1.26–1.09 (m, 8H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 143.3, 136.9, 129.6, 127.0, 43.1, 29.4, 28.7, 26.2, 21.5; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₃₂N₂O₄S₂ [M+H]⁺: , 454.1960, found: 454.1960
TLC Rf (hexanes/ethyl acetate 2/1) 0.15
SI, pp. 45, 134–135
S10
¹H NMR (600 MHz, CDCl₃) δ 7.73 (d, J = 8.3 Hz, 4H), 7.32–7.28 (m, 4H), 5.03 (t, J = 6.5 Hz, 2H), 2.81–2.73 (m, 2H), 2.67 (ddd, J = 12.6, 7.4, 6.4 Hz, 2H), 2.42 (s, 6H), 1.80 (dt, J = 12.8, 1.9 Hz, 1H), 1.71–1.67 (m, 1H), 1.66–1.59 (m, 2H), 1.44–1.36 (m, 2H), 1.24–1.03 (m, 1H), 0.74 (qd, J = 12.8, 3.7 Hz, 2H), 0.47 (q, J = 12.1 Hz, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 143.27, 136.91, 129.64, 127.04, 43.08, 29.35, 28.65, 26.16, 21.46; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₃₀N₂O₄S₂ [M+Na]⁺: 473.1545, found: 473.1534
TLC Rf (hexanes/ethyl acetate 1/1) 0.3
SI, pp. 46, 136–137
S10b
¹H NMR (600 MHz, CDCl₃) δ 4.61–4.56 (m, 2H), 2.95 (hept, J = 6.8 Hz, 4H), 1.81–1.69 (m, 4H), 1.43 (s, 18H), 1.24 (qt, J = 13.0, 3.6 Hz, 1H), 0.82 (qd, J = 12.8, 3.8 Hz, 2H), 0.57 (q, J = 12.2 Hz, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 156.1, 79.1, 46.9, 38.0, 34.7, 30.5, 28.4, 25.2; image data were not transcribed
SI, pp. 46, 138–139
S11
¹H NMR (400 MHz, CDCl₃) δ 7.72 (d, J = 8.3 Hz, 4H), 7.36 (d, J = 8.0 Hz, 4H), 2.99 (t, J = 7.0 Hz, 4H), 2.45 (s, 6H), 1.71–1.58 (m, 4H), 1.31 (d, J = 5.0 Hz, 8H); image caption specifies 600 MHz; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 144.25, 131.00, 129.81, 128.51, 51.78, 28.97, 26.86, 26.33, 21.57; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₃₄N₄O₄S₂ [M+H]⁺: 483.2100, found: 483.2094
TLC Rf (hexanes/ethyl acetate 1/2) 0.85
SI, pp. 47, 140–141
S12
¹H NMR (600 MHz, CDCl₃) δ 7.71 (d, J = 8.0 Hz, 4H), 7.37 (d, J = 7.8 Hz, 4H), 2.89 (s, 4H), 2.86–2.73 (m, 4H), 2.45 (s, 6H), 1.99–1.79 (m, 4H), 1.76 (dq, J = 7.4, 3.8 Hz, 2H), 1.26 (qd, J = 13.4, 6.8 Hz, 2H), 0.99–0.79 (m, 2H), 0.64 (q, J = 12.1 Hz, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 144.32, 130.81, 129.87, 128.47, 58.22, 35.20, 34.96, 30.73, 25.29, 21.57; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₃₂N₄O₄S₂ [M+H]⁺: 481.1943, found: 481.1951
TLC Rf (hexanes/ethyl acetate 1/2) 0.8
SI, pp. 48, 142–143
49
¹H NMR (600 MHz, CDCl₃) δ 8.54 (d, J = 2.1 Hz, 2H), 7.66–7.58 (m, 4H), 2.80–2.52 (m, 4H), 1.63 (t, J = 7.5 Hz, 4H), 1.38–1.25 (m, 8H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 145.84 (q, J = 34.7 Hz), 124.99–118.35 (m); image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −67.57; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₀H₂₂F₆N₂ [M+H]⁺: 405.1765, found: 405.1771
TLC Rf (hexanes/ethyl acetate 8/1) 0.7
SI, pp. 49, 144–146
50
¹H NMR (600 MHz, CDCl₃) δ 7.70 (s, 2H), 7.66 (s, 4H), 3.18–2.55 (m, 4H), 1.66 (t, J = 7.7 Hz, 4H), 1.34 (d, J = 3.1 Hz, 8H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 131.44 (q, J = 32.9 Hz), 123.46 (q, J = 272.5 Hz); image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −62.71
HRMS (ESI-TOF) Calculated for C₂₄H₂₂F₁₂ [M+H]⁺: 538.1530, not found
TLC Rf (hexanes/ethyl acetate 8/1) 0.85
SI, pp. 50, 147–148
51
¹H NMR (600 MHz, CDCl₃) δ 7.94 (d, J = 8.2 Hz, 4H), 7.17 (d, J = 8.2 Hz, 4H), 4.36 (q, J = 7.1 Hz, 4H), 2.76–2.32 (m, 4H), 1.84–1.61 (m, 4H), 1.53 (ddd, J = 11.0, 7.3, 3.6 Hz, 2H), 1.38 (t, J = 7.1 Hz, 6H), 1.20–1.03 (m, 1H), 0.85 (td, J = 12.5, 3.8 Hz, 2H), 0.72 (q, J = 12.0 Hz, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 166.70, 146.51, 129.40, 129.10, 128.06, , 60.74, 44.08, 39.94, 39.57, 32.59, 25.86, 14.35; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₆H₃₂O₄ [M+H]⁺: 409.2379, found: 409.2381
TLC Rf (hexanes/ethyl acetate 2/1) 0.15
SI, pp. 51, 149–150
52
¹H NMR (600 MHz, CDCl₃) δ 7.08 (d, J = 7.6 Hz, 4H), 7.01 (d, J = 7.7 Hz, 4H), 2.48 (dd, J = 13.4, 6.3 Hz, 2H), 2.38 (dd, J = 13.4, 7.7 Hz, 2H), 2.32 (s, 6H), 1.82–1.60 (m, 4H), 1.48 (ddd, J = 11.2, 7.3, 3.7 Hz, 2H), 1.12 (dtd, J = 19.3, 8.6, 4.9 Hz, 2H), 0.88–0.78 (m, 2H), 0.70 (q, J = 12.0 Hz, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 138.12, 134.89, 129.05, 128.72, 43.74, 40.21, 39.82, 32.74, 26.02, 20.99; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) Image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₂₈ [M+H]⁺: 294.2348, not found
TLC Rf (hexanes/ethyl acetate 8/1) 0.75
SI, pp. 52, 151–153
S13
¹H NMR (600 MHz, CDCl₃) δ 7.95–7.76 (m, 2H), 7.29 (d, J = 8.1 Hz, 2H), 4.03 (t, J = 6.1 Hz, 2H), 3.82–3.68 (m, 4H), 3.68–3.58 (m, 4H), 2.50 (t, J = 6.6 Hz, 2H), 2.44 (s, 3H), 1.45 (s, 9H), 1.32 (s, 9H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 170.9, 150.9, 144.0, 137.6, 129.2, 128.0, 84.3, 80.5, 70.3, 70.1, 69.3, 66.9, 45.4, 36.2, 28.1, 27.8, 21.6; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₃H₃₇NO₈S [M+Na]⁺: 510.2138, found: 510.2144
TLC Rf (pentane/ethyl acetate 2/1) 0.6
SI, pp. 53, 154–155
S14
¹H NMR (600 MHz, CDCl₃) δ 7.94–7.69 (m, 1H), 7.30 (d, J = 7.9 Hz, 1H), 5.64 (t, J = 6.0 Hz, 0H), 3.77 (t, J = 5.9 Hz, 1H), 3.70–3.46 (m, 3H), 3.09 (q, J = 5.4 Hz, 1H), 2.63 (t, J = 5.9 Hz, 1H), 2.42 (s, 2H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 174.89, 143.36, 136.84, 129.68, 127.12, 70.16, 70.02, 69.32, 66.44, 42.85, 34.68, 21.50; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₁₄H₂₁NO₆S [M−H]⁻: 330.1011, found: 330.1003
TLC Rf (ethyl acetate) 0.3
SI, pp. 54, 156–157
S15
¹H NMR (600 MHz, CDCl₃) δ 8.08–7.51 (m, 1H), 7.33–7.19 (m, 1H), 5.36 (t, J = 6.0 Hz, 0H), 3.85 (t, J = 6.1 Hz, 0H), 3.67–3.43 (m, 1H), 3.13 (q, J = 5.4 Hz, 0H), 2.93 (t, J = 6.1 Hz, 0H), 2.38 (s, 1H); image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 167.74, 161.83, 143.15, 137.12, 134.79, 129.57, 128.75, 127.00, 124.02, 70.56, 70.16, 69.25, 65.81, 42.95, 32.25, 21.41; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₂H₂₄N₂O₈S [M+Na]⁺: 499.1151, found: 499.1144
TLC Rf (hexanes/ethyl acetate 1/2) 0.5
SI, pp. 55, 158–159
S16
¹H NMR (600 MHz, CDCl₃) δ 8.65 (s, 1H), 7.84–7.70 (m, 3H), 7.63 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.3 Hz, 2H), 5.28 (m, J = 13.0, 6.0 Hz, 1H), 3.73 (t, J = 6.4 Hz, 2H), 3.62–3.49 (m, 6H), 3.20–3.09 (m, 2H), 3.01 (t, J = 6.4 Hz, 2H), 2.44 (s, 3H); image caption specifies a ¹³H spectrum; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 150.6, 146.3 (q, J = 35 Hz), 143.4, 138.1, 137.7, 137.0, 129.7, 127.1, 121.7 (q, J = 275 Hz), 120.1, 70.8, 70.2, 70.2, 69.5, 42.9, 33.2, 21.5; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −67.7; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₁₉H₂₄F₃N₂O₄S [M+H]⁺: 433.1409, found: 433.1407
TLC Rf (hexanes/acetone 2/1) 0.49
SI, pp. 56, 160–162
S17
¹H NMR (600 MHz, CDCl₃) δ 8.62 (s, 1H), 7.83–7.74 (m, 3H), 7.63 (d, J = 8.1 Hz, 1H), 7.37 (d, J = 8.3 Hz, 2H), 3.78–3.71 (m, 4H), 3.64–3.58 (m, 4H), 3.32 (t, J = 5.6 Hz, 2H), 2.98 (t, J = 6.4 Hz, 2H), 2.46 (s, 3H); image caption specifies a ¹³H spectrum; image data were not transcribed
¹³C NMR (151 MHz, CDCl₃) δ 150.5, 146.2 (q, J = 35 Hz), 144.3, 138.3, 137.8, 131.7, 129.8, 128.5, 121.7 (q, J = 273 Hz), 120.1 (d, J = 3 Hz), 70.8, 70.3, 70.3, 69.0, 51.6, 33.2, 21.6; image data were not transcribed
¹⁹F NMR (376 MHz, CDCl₃) δ −67.7; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₁₉H₂₅F₃N₃O₄S [M+H]⁺: 448.1518, found: 448.1508
TLC Rf (DCM/ether 1/1) 0.78
SI, pp. 57, 163–165
S18
¹H NMR (600 MHz, MeOD) δ 8.60 (s, 1H), 7.91 (d, J = 8.1 Hz, 1H), 7.76–7.67 (m, 2H), 7.47 (s, 1H), 7.42 (d, J = 7.8 Hz, 1H), 5.16 (dd, J = 13.3, 5.1 Hz, 1H), 4.52–4.39 (m, 2H), 3.77–3.67 (m, 4H), 3.01–2.86 (m, 5H), 2.84–2.74 (m, 1H), 2.55–2.44 (m, 1H), 2.22–2.13 (m, 1H); image caption specifies a ¹³H spectrum; image data were not transcribed
¹³C NMR (151 MHz, MeOD) δ 173.3, 170.8, 170.1, 150.3, 145.3 (q, J = 33 Hz) 144.6, 142.6, 139.5, 138.3, 129.4, 128.9, 123.5, 122.8, 121.8 (q, J = 397 Hz), 120.0 (d, J = 3 Hz), 71.3, 70.3, 70.0, 69.9, 52.2, 36.0, 32.6, 31.0, 22.7; image data were not transcribed
¹⁹F NMR (376 MHz, MeOD) δ −69.0; image data were not transcribed
HRMS (ESI-TOF) Calculated for C₂₅H₂₇F₃N₃O₅ [M+H]⁺: 506.1903, found: 506.1895