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75.0, 74.5, 72.7, 66.6, 55.2, 50.2, 36.6, 31.3, 31.2, 23.3, 21.3; HRMS
(ESI) calcd for C24H30O4SNa [(M + Na)+] 437.1757, found 437.1757.
( )-3d. Synthesized from ( )-2d according to GP2 except that the
reaction was performed in CH2Cl2 at room temperature: IR (film)
2865, 1707, 1463, 1106, 1068, 1044, 687 cm−1; H NMR (600 MHz,
CDCl3) δ 7.34−7.29 (m, 4H), 7.27−7.22 (m, 3H), 7.18−7.15 (m,
2H), 4.61 (d, J = 12.4 Hz, 1H), 4.57 (d, J = 12.4 Hz, 1H), 4.36 (dddd,
J = 12.0, 7.2, 6.2, 2.1 Hz, 1H), 4.32 (dddd, J = 3.2, 3.1, 2.8, 2.4 Hz,
1H), 4.13 (dddd, J = 11.7, 5.2, 4.8, 2.1 Hz, 1H), 3.48−3.45 (m, 2H),
2.93 (dd, J = 14.4, 7.2 Hz, 1H), 2.66 (dd, J = 14.4, 6.2 Hz, 1H), 2.34
(s, 3H), 1.74 (dddd, J = 13.4, 3.2, 2.1, 1.4 Hz, 1H), 1.60 (dddd, J =
13.4, 3.1, 2.1, 1.4 Hz, 1H), 1.51 (ddd, J = 13.4, 11.7, 2.8 Hz, 1H), 1.48
(ddd, J = 13.4, 12.0, 2.4, Hz, 1H), 1.04 (s, 18H), 1.03 (s, 3H); 13C
NMR (150 MHz, CDCl3) δ 195.4, 139.5, 138.6, 134.4 (2C), 129.9
(2C), 128.3 (2C), 127.6 (2C), 127.4, 124.4, 73.34, 73.27, 71.7, 69.0,
64.7, 50.0, 38.9, 35.6, 21.3, 18.1 (6C), 12.2 (3C); HRMS (ESI) calcd
for C31H46O4SSiNa [(M + Na)+] 565.2778, found 565.2761.
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2935, 2857, 1703, 1513, 1249, 1089, 826 cm−1; H NMR (600 MHz,
C6D6) δ 7.37−7.34 (m, 2H), 7.27−7.24 (m, 2H), 6.82−6.79 (m, 2H),
6.69−6.67 (m, 2H), 4.39 (s, 2H), 3.78 (m, 1H), 3.66 (m, 1H), 3.57
(m, 1H), 3.43 (m, 1H), 3.29 (s, 3H), 3.16 (s, 3H), 2.79 (dd, J = 14.8,
7.9 Hz, 1H), 2.43 (dd, J = 14.8, 4.8 Hz, 1H), 1.83 (m, 1H), 1.74 (m,
1H), 1.47 (m, 1H), 1.30−1.23 (m, 2H), 1.18 (m, 1H), 1.07−0.95 (m,
2H); 13C NMR (150 MHz, CDCl3) δ 196.3, 160.5, 159.0, 136.0 (2C),
130.7, 129.2 (2C), 118.6, 114.8 (2C), 113.7 (2C), 75.0, 74.5, 72.6,
66.6, 55.3, 55.2, 50.1, 36.6, 31.3, 31.2, 23.4; HRMS (ESI) calcd for
C24H30O5SNa [(M + Na)+] 453.1706, found 453.1708.
(−)-24. According to GP2, (−)-24 was synthesized from (+)-17
(reaction time: 4.5 h): [α]30 −1.5 (c 1.00, CHCl3); IR (film) 2928,
( )-3e. Synthesized from ( )-2e according to GP2 except that the
reaction was performed in CH2Cl2 at room temperature: IR (film)
D
1
2856, 1706, 1389, 1252, 1110, 741, 702 cm−1; H NMR (600 MHz,
1
2933, 2856, 1709, 1517, 1343, 1088, 852, 743 cm−1; H NMR (600
CDCl3) δ 7.67−7.64 (m, 4H), 7.42−7.38 (m, 2H), 7.37−7.34 (m,
4H), 7.26−7.23 (m, 2H), 7.18−7.15 (m, 2H), 3.79 (ddd, J = 11.0, 9.7,
4.8 Hz, 1H), 3.73 (dddd, J = 12.7, 7.6, 5.2, 2.4 Hz, 1H), 3.68 (ddd, J =
10.3, 6.2, 5.9 Hz, 1H), 3.63 (ddd, J = 10.3, 6.2, 5.9 Hz, 1H), 3.25 (m,
1H), 2.87 (dd, J = 14.8, 7.6 Hz, 1H), 2.62 (dd, J = 14.8, 5.2 Hz, 1H),
2.34 (s, 3H), 1.72−1.65 (m, 2H), 1.63−1.52 (m, 3H), 1.45−1.39 (m,
2H), 1.04 (s, 9H), 0.87 (s, 9H), 0.83 (d, J = 6.8 Hz, 3H), 0.04 (s, 3H),
0.03 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 195.9, 139.7, 135.7
(4C), 134.6 (2C), 134.1 (2C), 130.1 (2C), 129.6 (2C), 127.7 (4C),
124.4, 78.8, 72.8, 71.4, 64.0, 49.7, 39.0, 35.7, 29.19, 29.15, 27.0 (3C),
25.9 (3C), 21.4, 19.3, 18.2, 5.2, −4.5, −4.6; HRMS (ESI) calcd for
C40H58O4SSi2Na [(M + Na)+] 713.3487, found 713.3499.
MHz, C6D6) δ 7.71−7.68 (m, 2H), 7.23−7.20 (m, 2H), 7.08−7.05 (m,
2H), 6.81−6.78 (m, 2H), 4.36 (s, 2H), 3.67 (dddd, J = 12.7, 8.6, 4.1,
2.0 Hz, 1H), 3.61 (m, 1H), 3.51 (m, 1H), 3.42 (dddd, J = 12.7, 8.3,
4.1, 1.7 Hz, 1H), 3.29 (s, 3H), 2.63 (dd, J = 14.8, 8.6 Hz, 1H), 2.30
(dd, J = 14.8, 4.1 Hz, 1H), 1.82 (m, 1H), 1.72 (m, 1H), 1.48 (m, 1H),
1.26 (m, 1H), 1.12−1.20 (m, 2H), 1.02 (m, 1H), 0.95 (m, 1H); 13C
NMR (150 MHz, CDCl3) δ 193.2, 159.1, 148.0, 136.5, 134.6 (2C),
130.6, 129.0 (2C), 123.9 (2C), 113.7 (2C), 75.0, 74.4, 72.6, 66.5, 55.2,
50.7, 36.5, 31.2 (2C), 23.3; HRMS (ESI) calcd for C23H27NO6SNa
[(M + Na)+] 468.1451, found 468.1449.
( )-3f. Synthesized from ( )-2f according to GP2 except that the
reaction was performed in CH2Cl2 at room temperature: IR (film)
(+)-25. According to GP2, (+)-25 was synthesized from (+)-18
1
2933, 2856, 1703, 1512, 1247, 1088, 814, 746 cm−1; H NMR (600
(reaction time: 23 h): [α]22 +23.7 (c 1.00, CHCl3); IR (film) 3444,
D
2936, 2851, 1683, 1630, 1439, 1094, 1043, 807 cm−1; H NMR (600
1
MHz, CDCl3) δ 7.91 (s, 1H), 7.84−7.82 (m, 2H), 7.78 (d, J = 7.9 Hz,
1H), 7.52−7.46 (m, 2H), 7.42 (dd, J = 8.6, 1.7 Hz, 1H), 7.21 (m, 2H),
6.82 (m, 2H), 4.41 (d, J = 11.3 Hz, 1H), 4.38 (d, J = 11.3 Hz, 1H),
3.84 (dddd, J = 13.0, 7.9, 5.2, 2.0 Hz, 1H), 3.74 (s, 3H), 3.62−3.54 (m,
2H), 3.50 (dddd, J = 12.7, 8.2, 4.1, 1.7 Hz, 1H), 2.89 (dd, J = 14.4, 7.9
Hz, 1H), 2.69 (dd, J = 14.4, 5.2 Hz, 1H), 1.83 (m, 1H), 1.79−1.68 (m,
2H), 1.66 (m, 1H), 1.58−1.49 (m, 2H), 1.30−1.18 (m, 2H); 13C
NMR (150 MHz, CDCl3) δ 195.5, 159.0, 134.1, 133.5, 133.3, 130.9,
130.7, 129.2 (2C), 128.7, 127.9, 127.7, 127.1, 126.5, 125.3, 113.7 (2C),
75.0, 74.5, 72.7, 66.6, 55.2, 50.4, 36.6, 31.3, 31.2, 23.3; HRMS (ESI)
calcd for C27H30O4SNa [(M + Na)+] 473.1757, found 473.1751.
( )-21: IR (film) 2931, 2856, 1705, 1427, 1110, 996, 806, 703
MHz, C6D6) δ 7.34−7.32 (m, 2H), 6.88−6.85 (m, 2H), 3.80 (dddd,
J = 12.7, 7.6, 5.2, 2.4 Hz, 1H), 3.66 (apparent dd, J = 11.3, 4.8 Hz,
1H), 3.05 (ddd, J = 12.0, 11.3, 2.4, Hz, 1H), 2.90 (ddd, J = 10.6, 8.9,
4.5 Hz, 1H), 2.78 (ddd, J = 10.6, 8.9, 4.8 Hz, 1H), 2.77 (dd, J = 15.1,
7.6 Hz, 1H), 2.37 (dd, J = 15.1, 5.2 Hz, 1H), 1.96 (s, 3H), 1.88−1.82
(m, 2H), 1.45−1.27 (m, 4H), 1.19−1.12 (m, 2H); 13C NMR (150
MHz, CDCl3) δ 195.5, 139.7, 134.4 (2C), 130.0 (2C), 124.1, 78.3,
78.0, 74.0, 68.0, 49.4, 30.9, 29.5, 29.4, 25.7, 21.3; HRMS (ESI) calcd
for C17H22O3SNa [(M + Na)+] 329.1182, found 329.1172.
(+)-26. According to GP2, (+)-26 was synthesized from (+)-19
(reaction time: 10.5 h): [α]29D +20.2 (c 1.00, CHCl3); IR (film) 3450,
1
cm−1; H NMR (600 MHz, C6D6) δ 7.82 (m, 4H), 7.32−7.21 (m,
1
2943, 2865, 1703, 1100, 959, 808, 767 cm−1; H NMR (600 MHz,
8H), 6.88−6.86 (m, 2H), 3.95 (m, 1H), 3.88 (ddd, J = 11.0, 6.2, 5.8
Hz, 1H), 3.74 (apparent ddd, J = 11.3, 7.3, 5.9 Hz, 1H), 3.41 (dddd,
J = 12.4, 9.2, 3.7, 1.7 Hz, 1H), 2.77 (dd, J = 14.5, 7.3 Hz, 1H), 2.43
(dd, J = 14.5, 5.9 Hz, 1H), 1.98 (s, 3H), 1.81 (m, 1H), 1.69 (m, 1H),
1.46 (m, 1H), 1.33 (m, 1H), 1.25−1.12 (m, 11H), 1.05−0.95 (m, 2H);
13C NMR (150 MHz, CDCl3) δ 195.8, 139.5, 135.5 (4C), 134.4 (2C),
134.1, 134.0, 129.9 (2C), 129.5 (2C), 127.6 (4C), 124.3, 74.8, 74.3,
60.4, 50.2, 39.4, 31.3, 31.2, 26.9 (3C), 23.4, 21.3, 19.2; HRMS (ESI)
calcd for C32H40O3SSiNa [(M + Na)+] 555.2360, found 555.2375.
(−)-22.: According to GP2, (−)-22 was synthesized from (−)-15
CDCl3) δ 7.27−7.25 (m, 2H), 7.20−7.17 (m, 2H), 4.31 (dddd, J =
13.4, 7.6, 5.2, 2.4 Hz, 1H), 4.08 (ddd, J = 3.1, 2.8, 2.8 Hz, 1H), 3.92
(m, 1H), 3.60 (ddd, J = 11.3, 9.3, 2.8 Hz, 1H), 3.44 (m, 1H), 3.00 (dd,
J = 9.3, 2.8 Hz, 1H), 2.84 (dd, J = 15.1, 7.6 Hz, 1H), 2.64 (dd, J = 15.1,
5.2 Hz, 1H), 2.35 (s, 3H), 2.29 (br s, 1H), 2.04 (m, 1H), 1.96 (ddd,
J = 14.1, 3.1, 2.4 Hz, 1H), 1.72−1.58 (m, 3H), 1.42 (m, 1H); 13C
NMR (150 MHz, CDCl3) δ 195.1, 139.6, 134.4 (2C), 130.0 (2C),
124.2, 79.7, 70.8, 68.8, 68.2, 65.7, 49.1, 37.2, 29.3, 25.5, 21.3; HRMS
(ESI) calcd for C17H22O4SNa [(M + Na)+] 345.1131, found 345.1139.
(+)-27. According to GP2, (+)-27 was synthesized from (−)-20
(reaction time: 7.5 h): [α]29 −3.2 (c 1.00, CHCl3); IR (film) 2942,
(reaction time: 10 h): [α]27 +31.5 (c 1.00, CHCl3); IR (film) 3446,
D
D
1
2864, 1463, 1112, 806, 702 cm−1; H NMR (600 MHz, CDCl3) δ
1
2942, 2920, 1700, 1100, 963, 808, 756 cm−1; H NMR (600 MHz,
7.64−7.61 (m, 4H), 7.39−7.36 (m, 2H), 7.35−7.31 (m, 4H), 7.20−
7.19 (m, 2H), 7.16−7.13 (m, 2H), 3.84 (dddd, J = 11.3, 11.3, 4.8, 4.8
Hz, 1H), 3.80−3.75 (m, 2H), 3.72 (dddd, J = 12.1, 7.6, 5.5, 2.4 Hz,
1H), 3.49 (dddd, J = 11.3, 8.3, 4.1, 2.4 Hz, 1H), 2.85 (dd, J = 14.8, 7.6
Hz, 1H), 2.64 (dd, J = 14.8, 5.5 Hz, 1H), 2.35 (s, 3H), 1.96 (ddd, J =
12.7, 4.8, 2.4 Hz, 1H), 1.88 (ddd, J = 12.7, 4.8, 2.4 Hz, 1H), 1.80 (m,
1H), 1.69 (m, 1H), 1.26 (ddd, J = 12.7, 12.1, 11.3 Hz, 1H), 1.24 (ddd,
J = 12.7, 11.3, 11.3 Hz, 1H), 1.04−1.02 (m, 21H), 1.01 (s, 9H); 13C
NMR (150 MHz, CDCl3) δ 195.6, 139.6, 135.5 (4C), 134.4 (2C),
133.98, 133.96, 123.0 (2C), 129.52, 129.50, 127.6 (4C), 124.2, 72.6,
72.1, 68.4, 60.5, 49.7, 41.7, 41.4, 38.9, 26.9 (3C), 21.3, 19.2, 18.1 (6C),
12.3 (3C); HRMS (ESI) calcd for C41H60O4SSi2Na [(M + Na)+]
727.3643, found 727.3665.
CDCl3) δ 7.27−7.25 (m, 2H), 7.21−7.18 (m, 2H), 3.96 (dddd, J =
12.7, 7.2, 5.5, 1.7 Hz, 1H), 3.92 (m, 1H), 3.70 (ddd, J = 11.3, 8.9, 5.2
Hz, 1H), 3.37 (m, 1H), 3.04 (ddd, J = 11.3, 8.9, 4.2 Hz, 1H), 2.93 (dd,
J = 15.1, 7.2 Hz, 1H), 2.83 (dd, J = 8.9, 8.9 Hz, 1H), 2.70 (dd, J = 15.1,
5.5 Hz, 1H), 2.57 (br s, 1H), 2.35 (s, 3H), 2.09 (ddd, J = 12.7, 5.2, 1.7
Hz, 1H), 2.03 (m, 1H), 1.70−1.65 (m, 2H), 1.50−1.42 (m, 2H); 13C
NMR (150 MHz, CDCl3) δ 195.2, 139.8, 134.4 (2C), 130.0 (2C),
123.4, 83.7, 75.0, 72.0, 70.1, 67.9, 49.0, 38.4, 29.0, 25.4, 21.3; HRMS
(ESI) calcd for C17H22O4SNa [(M + Na)+] 345.1131, found 345.1140.
α,β-Unsaturated Amide/Imide Derivatives 28a−g and 30−
42. ( )-28a. According to GP1, ( )-28a was prepared from ( )-4
and 1-(2-propenoyl)-pyrrolidine:56 IR (film) 3420, 2951, 2873, 1651,
1
1609, 1437, 1375, 1111, 981 cm−1; H NMR (600 MHz, CDCl3) δ
(+)-23. According to GP2, (+)-23 was synthesized from (−)-16
7.67−7.64 (m, 4H), 7.44−7.34 (m, 5H), 6.85 (ddd, J = 15.0, 7.2,
6.6 Hz, 1H), 6.08 (d, J = 15.0 Hz, 1H), 3.90−3.80 (m, 3H), 3.52−3.46
(reaction time: 6 h): [α]27 +14.7 (c 1.00, CHCl3); IR (film) 2942,
D
2599
dx.doi.org/10.1021/jo202179s | J. Org. Chem. 2012, 77, 2588−2607