58
Werness JB, et al. Sci China Chem January (2011) Vol.54 No.1
Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 21.7, 25.0, 34.9,
43.0, 53.0,76.3,82.4,111.8,127.3,130.0,137.1,142.3,143.6.
IR: ν 3304, 2965, 1611, 1566, 1421, 1332, 1302, 1154, 1087
cm−1. HRMS (ESI) for C16H21NO2S (M+H), 292.1366
(calcd), found 292.1362.
7.31 (d, J = 8.5 Hz, 2H), 7.73 (d, J = 8.5 Hz, 2H). 13C NMR
(100 Hz, CDCl3): δ 24.5, 28.9, 29.2, 31.7, 37.4, 48.7, 58.2,
100.9, 109.1, 127.7, 129.9, 135.0, 143.6, 196.2. IR: ν 3195,
2948, 1738, 1732, 1455, 1349, 1216, 1161, 1093 cm−1.
HRMS (ESI) for C18H24BrNO2S (M+H), 398.078389
(calcd), found 398.07783.
9b 1H NMR (500 MHz, CDCl3, TMS): δ0.94(s,6H),2.09
(d, J = 8.0 Hz, 2H), 2.80 (s, 1H), 2.88 (d, J = 6.5 Hz, 2H), 5.39
(t, J = 6.5 Hz, 1H), 5.47 (d, J = 16 Hz, 1H), 6.14 (dt, J = 7.5,
16 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H),
8.67 (s, 1H). 13C NMR (100 Hz, CDCl3): δ 25.0, 35.1, 43.0,
53.5, 76.8, 82.1, 112.3, 121.0, 127.4, 132.9, 139.1, 141.4,
141.5, 150.1. IR: ν 3349, 3101, 2662, 1543, 1418, 1382,
1361, 1186, 1169, 1064 cm−1. HRMS (ESI) for
C15H17N3O6S (M+H), 368.0911 (calcd), found 368.0909.
1
10a Minor diastereomer: H NMR (500 MHz, CDCl3): δ
1.19 (s, 9H), 1.6−1.9 (m, 4H), 2.43 (s, 3H), 3.1−3.2 (m, 1H),
3.5−3.6 (m, 1H), 4.32−4.36 (m, 1H), 5.44 (d, J = 5.0 Hz,
1H), 7.31 (d, J = 8.5 Hz, 2H), 7.72 (d, J = 8.5 Hz, 2H). 13C
NMR (100 Hz, CDCl3): δ 24.1, 29.3, 29.7, 31.1, 37.4, 48.7,
58.2, 100.7, 108.5, 127.6, 129.9, 135.2, 143.7, 196.8.
1
10b Major diastereomer: H NMR (500 MHz, CDCl3): δ
1.08 (s, 3H), 1.13 (s, 9H), 1.15 (s, 3H), 1.69 (dd, J = 13.0,
9.0 Hz, 1H), 2.02 (ddd, J = 12.5, 7.0, 1.5 Hz, 1H), 3.26 (d, J
= 10.5 Hz, 1H), 3.63 (dd, J = 10.5, 1.5 Hz, 1H), 4.57 (ddd, J
= 8.5, 7.5, 7.5 Hz, 1H), 4.96 (d, J = 8.0 Hz, 1H), 8.46−8.55
(m, 3H). 13C NMR (125 Hz, CDCl3): δ 25.6, 29.7, 37.0,
38.2, 59.5, 62.0, 98.7, 107.7, 119.7, 126.8, 133.9, 139.6,
147.9, 149.7, 178.1, 197.3. IR: ν 3105, 2968, 1555, 1539,
1460, 1363, 1162, 1107, 1064 cm−1. HRMS (ESI) for
C19H24BrN3O6S (M+H), 502.0642 (calcd), found 502.0645.
10b Minor diastereomer: 1H NMR (500 MHz, CDCl3): δ
1.02 (s, 3H), 1.15 (s, 9H), 1.16 (s, 3H), 1.77 (dd, J = 12.5,
8.0 Hz, 1H), 2.03 (ddd, J = 12.5, 7.5, 1.5 Hz, 1H), 3.22 (d, J
= 10.5 Hz, 1H), 3.48 (dd, J = 10.5, 1.5 Hz, 1H), 4.69 (ddd, J
= 8.0, 7.5, 6.5 Hz, 1H), 5.32 (d, J = 6.5 Hz, 1H), 8.24 (d, J =
8.0 Hz, 1H), 8.42–8.50 (m, 2H).
1
9c H NMR (400 MHz, CDCl3, TMS): δ 0.89 (s, 6H),
2.04 (d, J = 8.4 Hz, 2H), 2.75 (d, J = 6.4 Hz, 2H), 2.81
(d, J = 2.0 Hz, 1H), 5.13 (t, J = 6.8 Hz, 1H), 5.43 (dd, J =
1.2, 15.6 Hz, 1H), 6.11 (dt, J = 8.0, 15.6 Hz, 1H), 8.06 (d,
J = 8.8 Hz, 2H), 8.38 (d, J = 8.8 Hz, 2H). 13C NMR (100
MHz, CDCl3): δ 25.0, 35.0, 42.9, 53.0, 76.8, 82.1, 112.2,
124.8, 128.5, 141.8, 145.9, 150.3. IR: ν 3300, 2960, 1607,
1530, 1424, 1349, 1311, 1164, 1092 cm−1. HRMS (ESI)
for C15H18N2O4S (M+H), 323.106004 (calcd), found
323.105800.
2.3 Synthesis of bromoallenyl pyrrolidines 10 and 11
General procedure (Scheme 3): To a solution of sulfona-
mide 7 or 9 in CHCl3 or CDCl3 (0.1 M) was added DABCO
(10 mol%) and NBS (1.2 equiv). The reaction was stirred at
room temperature until the starting material was consumed
(10 min to 72 h). The solvent was evaporated and the resi-
due was purified by column chromatography on silica gel to
afford bromoallenyl pyrrolidines 10 and 11 in 70%−88%
yield.
11a Major diasteromer: 1H NMR (500 MHz, CDCl3): δ
1.08 (s, 6H), 1.55 (s, 1H), 1.70−1.81 (m, 2H), 2.44 (s, 3H),
3.07 (d, J = 10.0 Hz, 1H), 3.21 (d, J = 10.0 Hz, 1H), 4.16
(dddd, J = 9.5, 8.5, 7.0, 2.0 Hz, 1H), 5.70 (dd, J = 6.0, 6.0
Hz, 1H), 6.01 (dd, J = 5.5, 1.5 Hz, 1H), 7.33 (d, J = 8.0 Hz,
2H), 7.74 (d, J = 8.0 Hz, 2H). 13C NMR (125 Hz, CDCl3): δ
21.8, 26.8, 37.9, 46.3, 57.7, 61.6, 74.4, 103.5, 127.9, 130.0,
134.8, 143.9, 201.5. IR: ν 3119, 2972, 2362, 1739, 1366,
1217, 1138, 1075 cm−1. HRMS (ESI) for C16H20BrNO2S
(M+H), 370.047089 (calcd), found 370.04677
1
10a Major diastereomer: H NMR (500 MHz, CDCl3): δ
1.21 (s, 9H), 1.6−1.9 (m, 4H), 2.43 (s, 3H), 3.1−3.2 (m, 1H),
3.4–3.5 (m, 1H), 4.25−4.27 (m, 1H), 5.41 (d, J = 5.0 Hz, 1H),
11a Minor diasteromer: 1H NMR (500 MHz, CDCl3): δ
1.10 (s, 6H), 1.55 (s, 1H), 1.70-1.81 (m, 2H), 2.44 (s, 3H),
3.02 (d, J = 10.0 Hz, 1H), 3.20 (d, J = 10.0 Hz, 1H), 4.21
(ddd, J = 9.5, 8.5, 7.0, 2.0 Hz, 1H), 5.68 (dd, J = 6.0, 6.0 Hz,
1H), 6.12 (dd, J = 5.5, 1.5 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H),
7.71 (d, J = 8.0 Hz, 2H). 13C NMR (125 Hz, CDCl3): δ 21.8,
26.8, 37.9, 46.2, 57.5, 61.5, 74.4, 103.8, 127.8, 129.9, 134.7,
143.8, 201.3.
11b Major diastereomer: 1H NMR (500 MHz, CDCl3): δ
0.82 (s, 3H), 1.11 (s, 3H), 1.72 (dd, J = 13.0, 7.5 Hz, 1H),
1.87 (dd, J =13.0, 7.5 Hz, 1H), 3.12 (d, J = 9.5 Hz, 1H),
3.21 (d, J = 9.5 Hz, 1H), 4.27 (dddd, J = 7.5, 7.5, 6.5, 1.5
Hz, 1H), 5.51 (dd, J = 6.5, 5.5 Hz, 1H), 6.03 (dd, J = 5.5,
1.5 Hz, 1H), 8.42 (d, J = 9.0 Hz, 1H), 8.38−8.40 (m, 2H).
13C NMR (100 Hz, CDCl3): δ 26.1, 37.8, 46.5, 58.5, 61.9,
74.5, 103.1, 120.7, 127.3, 133.5, 143.0, 148.1, 150.1, 201.6.
IR: ν 3070, 2962, 1960, 1606, 1530, 1468, 1350, 1313, 1194,
Scheme 3 Synthesis of bromoallenyl pyrrolidines via 1,4-addition of
sulfonamides and bromine to 1,3-enynes.