I
B. Formánek et al.
Paper
Synthesis
Yield: 41.9 mg (90%); yellow-green foam; 62% ee (IC, heptane/i-PrOH,
80:20; tR = 12.9 (major), 16.7 (minor) min); [α]D = +12.9° (c 0.52; CH-
Cl3).
1H NMR (600 MHz, CDCl3): δ (mixture of rotamers, 1:1) = 8.30 (d, J =
7.7 Hz, 1 H), 8.23 (d, J = 7.4 Hz, 2 H), 8.04 (d, J = 8.7 Hz, 1 H), 7.86 (d,
J = 7.9 Hz, 2 H), 7.50–7.45 (m, 6 H), 7.35–7.27 (m, 5 H), 7.24–7.12 (m,
7 H), 7.02–6.99 (m, 1 H), 6.96–6.94 (m, 1 H), 6.77 (s, 1 H), 6.63 (s, 1 H),
6.41 (s, 1 H), 6.39 (s, 1 H), 5.97 (s, 1 H), 5.51 (s, 1 H), 3.69 (s, 3 H), 3.57
(s, 3 H).
13C NMR (151 MHz, CDCl3): δ (mixture of rotamers, 0.7:1) = 167.0,
166.2, 148.33, 148.28, 143.8, 142.7, 142.6, 142.4, 141.3, 139.0, 137.8,
136.6, 134.4, 134.0, 133.5, 133.0, 131.0, 130.7, 130.6, 130.3, 129.4
(2C), 129.3 (2C), 129.0, 128.7, 126.7, 126.0, 125.93, 125.90, 125.8,
125.5, 125.4, 125.0, 122.9, 121.3, 121.3, 121.2, 116.9 (2C), 115.9 (2C),
65.6, 63.4, 52.2, 52.1.
IR (KBr): 3061, 2951, 2852, 1717, 1592, 1512, 1338, 1238, 1145, 735
cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C23H19O4N2BrNaS+: 521.0141;
13C NMR (151 MHz, CDCl3): δ (mixture of rotamers, 1:1) = 166.8,
166.0, 148.1, 147.9, 147.4, 146.6, 143.3, 143.0, 142.8, 142.6, 142.0,
138.7, 136.3, 134.4, 133.6, 133.3, 131.5 (2C), 129.5 (4C), 128.5 (2C),
127.5, 125.9, 125.77, 125.76, 125.7, 125.6, 125.5, 125.4, 124.0 (2C),
122.5 (2C), 121.7, 121.6, 116.9 (2C), 116.0 (2C), 65.4, 63.7, 52.32 (2C
overlapped).
found: 521.0141.
Methyl (R)-2-(((4-Nitrophenyl)((2-nitrophenyl)thio)amino)(phe-
nyl)methyl)acrylate (14h)
By following GP4, the reaction was carried out with 9a (43.8 mg, 0.15
mmol) and 5b (29.1 mg, 0.10 mmol). FC (hexanes/EtOAc, 5:1) fur-
nished 14h.
IR (KBr): 3069, 2952, 2853, 1716, 1592, 1518, 1344, 1235, 1147, 857
cm–1
.
Yield: 44.6 mg (96%); yellow-green foam; 52% ee (IA, heptane/i-PrOH,
80:20; tR = 8.5 (minor), 16.5 (major) min); [α]D = –5.7° (c 0.44; CHCl3).
HRMS (ESI): m/z [M + Na]+ calcd for C23H19N3NaO6S+: 488.0887;
found: 488.0886.
1H NMR (600 MHz, CDCl3): δ (mixture of rotamers, 1:1) = 8.36–8.33
(m, 1 H), 8.20–8.17 (m, 2 H), 8.12–8.09 (m, 2 H), 8.07–8.04 (m, 1 H),
7.55–7.51 (m, 1 H), 7.42–7.12 (m, 16 H), 7.04–6.98 (m, 3 H), 6.77 (m,
1 H), 6.56 (m, 1 H), 6.45 (m, 1 H), 6.37 (m, 1 H), 5.83 (m, 1 H), 5.59 (m,
1 H), 3.72 (s, 3 H), 3.53 (s, 3 H).
13C NMR (151 MHz, CDCl3): δ (mixture of rotamers, 1:1) = 167.0,
166.1, 154.3, 154.0, 142.8, 142.70, 141.41, 141.39, 141.37, 140.5,
138.7, 137.2, 136.9, 135.1, 134.2, 133.9, 133.4, 130.9 (2C), 129.1 (2C),
128.7, 128.0, 127.5 (2C), 127.2 (2C), 126.1, 126.0, 125.9, 125.8, 125.6
(2C), 125.50 (2C), 125.48 (2C), 125.3, 116.3 (2C), 115.7 (2C), 66.7,
64.1, 52.4, 52.2.
Methyl (R)-2-((2-Bromophenyl)(((2-nitrophenyl)thio)(phe-
nyl)amino)methyl)acrylate (14f)
By following GP4, the reaction was carried out with 9f (55.7 mg, 0.15
mmol) and 5a (24.6 mg, 0.10 mmol). FC (hexanes/EtOAc, 10:1) fur-
nished 14f.
Yield: 47.9 mg (96%); yellowish oil; 30% ee (IC, heptane/i-PrOH, 99:1;
tR = 11.6 (minor), 13.9 (major) min); [α]D = +22.3° (c 0.47; CHCl3).
1H NMR (600 MHz, CDCl3): δ (mixture of rotamers, 0.6:1) = 8.30 (d, J =
7.9 Hz, 1 H), 7.99 (dd, J = 8.3, 1.4 Hz, 1 H), 7.62 (d, J = 7.9 Hz, 1 H),
7.54–7.48 (m, 4 H), 7.41–7.39 (m, 1 H), 7.37–7.28 (m, 6 H), 7.25–7.17
(m, 5 H), 7.11–7.08 (m, 3 H), 7.00–6.95 (m, 2 H), 6.90 (t, J = 7.3 Hz,
1 H), 6.82–6.79 (m, 3 H), 6.58 (d, J = 1.6 Hz, 1 H), 6.36 (s, 1 H), 5.90 (d,
J = 1.9 Hz, 1 H), 5.40 (s, 1 H), 3.66 (s, 3 H), 3.51 (s, 3 H).
IR (KBr): 3075, 2952, 2842, 1720, 1584, 1514, 1336, 1254, 1114, 1060
cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C23H19N3NaO6S+: 488.0887;
found: 488.0887.
13C NMR (151 MHz, CDCl3): δ (mixture of rotamers, 0.6:1) = 166.4,
166.3, 148.6, 147.9, 143.8, 142.7, 142.5, 142.4, 138.3, 137.4, 137.2,
135.7, 133.7, 133.62, 133.60, 133.1, 132.3, 132.0, 129.5, 129.4 (2C),
129.28, 129.26 (2C), 128.4, 127.9, 126.9, 126.5, 126.33, 126.28, 126.2,
125.8, 125.4, 125.2, 124.9, 123.4, 121.2, 121.1, 116.8 (2C), 115.8 (2C),
64.6, 64.4, 52.2, 52.0.
Ethyl (R)-2–4-((2-(Methoxycarbonyl)-1-phenylallyl)((2-nitrophe-
nyl)thio)amino)benzoate (14i)
By following GP4, the reaction was carried out with 9a (43.8 mg, 0.15
mmol) and 5c (31.8 mg, 0.10 mmol). FC (hexanes/EtOAc, 7:1) fur-
nished 14h.
IR (KBr): 3091, 2950, 2842, 1709, 1592, 1511, 1339, 1235, 1150, 757
Yield: 47.2 mg (96%); yellow-green foam; 52% ee (IA, heptane/i-PrOH,
80:20; tR = 7.9 (minor), 10.6 (major) min); [α]D = +26.9° (c 0.97; CH-
Cl3).
cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C23H19O4N2BrNaS+: 521.0141;
found: 521.0142.
1H NMR (600 MHz, CDCl3): δ (mixture of rotamers, 0.9:1) = 8.31 (d, J =
8.2 Hz, 1 H), 8.01 (d, J = 8.2 Hz, 1 H), 7.97 (d, J = 9.0 Hz, 2 H), 7.89 (d,
J = 9.0 Hz, 2 H), 7.48 (t, J = 7.6 Hz, 1 H), 7.38–7.35 (m, 3 H), 7.32–7.28
(m, 3 H), 7.25–7.17 (m, 9 H), 7.13 (t, J = 7.6 Hz, 1 H), 6.99–6.95 (m,
3 H), 6.74 (s, 1 H), 6.52 (s, 1 H), 6.40 (s, 1 H), 6.35 (s, 1 H), 5.82 (s, 1 H),
5.54 (s, 1 H), 4.37–4.28 (m, 4 H), 3.69 (s, 3 H), 3.51 (s, 3 H), 1.36 (t, J =
7.1 Hz, 3 H), 1.33 (t, J = 7.1 Hz, 3 H).
Methyl (R)-2-((3-Bromophenyl)(((2-nitrophenyl)thio)(phe-
nyl)amino)methyl)acrylate (14g)
By following GP4, the reaction was carried out with 9g (55.7 mg, 0.15
mmol) and 5a (24.6 mg, 0.10 mmol). FC (hexanes/EtOAc, 10:1) fur-
nished 14g.
Yield: 29.9 mg (60%); yellow foam; 63% ee (IC, heptane/i-PrOH, 99:1;
tR = 10.9 (major), 12.4 (minor) min); [α]D = +76.8° (c 0.63; CHCl3).
13C NMR (151 MHz, CDCl3): δ (mixture of rotamers, 0.9:1) = 167.0,
166.3, 166.2 (2C overlapped), 152.5, 152.3, 142.8, 142.69, 142.65,
141.7, 139.1, 137.9, 137.2, 134.8, 134.6, 133.7, 133.1, 131.2 (2C),
131.1 (2C), 130.9 (2C), 128.9 (2C), 128.4, 127.7, 127.4 (2C), 127.3 (2C),
125.92, 125.88 (2C overlapped), 125.8, 125.6, 125.4, 125.1, 123.0,
116.1 (2C), 115.4 (2C), 66.4, 63.9, 60.6, 60.5, 52.2, 52.1, 14.4, 14.3.
1H NMR (600 MHz, CDCl3): δ (mixture of rotamers, 0.7:1) = 8.29 (d, J =
8.1 Hz, 1 H), 8.04 (d, J = 8.1 Hz, 1 H), 7.50–7.38 (m, 6 H), 7.33–7.28 (m,
4 H), 7.24–7.14 (m, 10 H), 7.08 (d, J = 8.3 Hz, 1 H), 6.98 (t, J = 7.2 Hz,
1 H), 6.93 (t, J = 6.7 Hz, 1 H), 6.86 (t, J = 7.8 Hz, 1 H), 6.66 (s, 1 H), 6.57
(s, 1 H), 6.39 (s, 1 H), 6.25 (s, 1 H), 5.90 (s, 1 H), 5.56 (s, 1 H), 3.71 (s,
3 H), 3.55 (s, 3 H).
IR (KBr): 3061, 2986, 2848, 1712, 1601, 1506, 1337, 1281, 1245, 1182,
1108 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–N