M. Mizukami et al. / Tetrahedron 69 (2013) 4120e4138
4131
144.22 (C), 138.20 (C), 134.88 (C), 129.99 (CHꢂ2), 129.29 (CHꢂ2),
128.34 (CHꢂ2), 128.21 (CHꢂ2), 127.84 (CH), 122.95 (CH), 80.92
(CH2), 79.76 (CH2), 51.79 (CH3), 51.13 (CH), 50.07 (CH2), 21.17 (CH3).
4.3.6. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-9-methoxy-2-tosyl-2,3,4,5-
tetrahydro-1H-2-benzazepin-5-yl]-propenoate (32b). Amorphous: IR
(ATR) 3351, 2922,1659 cmꢀ1; MS (SIMSþ) m/z 432 (MþHþ), 400, 369,
277; HRMS m/z calcd for C22H26NO6S: 432.1479, found 432.1507; 1H
4.3.2. Methyl (2E,4SR)-4-(3-methoxyphenyl)-4-[(5RS)-3-
tosyloxazolidin-5-yl]-2-butenoate (28b). Pale yellow oil: IR (neat)
2956, 1723, 1659, 1601; EIMS m/z 431 (Mþ), 400, 226; HRMS m/z
calcd for C22H25NO6S: 431.1401, found 431.1422; 1H NMR (400 MHz,
NMR (400 MHz, CDCl3)
d
7.74 (d, J¼8.3 Hz, 2H), 7.32 (d, J¼8.3 Hz, 2H),
7.22 (t, J¼8.3 Hz, 1H), 7.07 (dd, J¼16.1, 5.4 Hz, 1H), 6.87 (d, J¼8.3 Hz,
1H), 6.78 (d, J¼8.3 Hz, 1H), 5.54 (d, J¼16.1 Hz, 1H), 5.35 (d, J¼14.2 Hz,
1H), 4.17e4.09 (m, 1H), 4.08e4.02 (m, 1H), 3.95 (d, J¼14.2 Hz, 1H),
3.87 (s, 3H), 3.69e3.67 (m, 1H), 3.68 (s, 3H), 3.11 (dd, J¼14.2, 1.5 Hz,
1H), 2.47 (d, J¼9.8 Hz, 1H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3)
CDCl3)
d
7.72 (d, J¼8.3 Hz, 2H), 7.37 (d, J¼8.3 Hz, 2H), 7.23 (t,
J¼7.8 Hz, 1H), 6.99 (dd, J¼15.6, 7.3 Hz, 1H), 6.81 (dd, J¼7.8, 2.4 Hz,
1H), 6.60 (d, J¼7.8 Hz, 1H), 6.55 (d, J¼2.4 Hz, 1H), 5.65 (d, J¼15.6 Hz,
1H), 5.06 (d, J¼5.9 Hz, 1H), 4.83 (d, J¼5.9 Hz, 1H), 4.04 (dd, J¼16.1,
7.3 Hz, 1H), 3.79 (s, 3H), 3.68 (s, 3H), 3.31 (dd, J¼12.7, 6.8 Hz, 1H),
d
166.51 (C), 157.03 (C), 146.05 (CH), 143.62 (C), 137.48 (C), 135.83 (C),
129.81 (CHꢂ2), 129.19 (CH), 128.18 (C), 127.29 (CHꢂ2), 122.99 (CH),
119.49 (CH), 111.14 (CH), 69.47 (CH), 56.26 (CH3), 54.72 (CH), 53.15
(CH2), 51.64 (CH3), 44.42 (CH2), 21.55 (CH3).
3.03e2.96 (m, 2H), 2.48 (s, 3H); 13C NMR (68 MHz, CDCl3)
d 166.42
(C), 160.06 (C), 146.93 (CH), 144.45 (C), 138.88 (C), 134.12 (C), 130.27
(CH), 129.92 (CHꢂ2), 127.93 (CHꢂ2), 122.69 (CH), 120.17 (CH),
114.30 (CH), 112.67 (CH), 80.87 (CH2), 79.51 (CH), 55.21 (CH3), 51.78
(CH), 51.55 (CH3), 50.04 (CH2), 21.61 (CH3).
4.3.7. Methyl (2E,4SR)-4-(3,4-dimethoxyphenyl)-4-[(5RS)-3-
tosyloxazolidin-5-yl]-2-butenoate (28c). Amorphous: IR (neat)
2956, 1723, 1657, 1597 cmꢀ1; EIMS m/z 461 (Mþ), 276, 262, 155;
HRMS m/z calcd for C23H27NO7S: 461.1507, found 461.1505; 1H NMR
4.3.3. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-8-methoxy-2-tosyl-2,3,4,5-
tetrahydro-1H-2-benzazepin-5-yl]-propenoate (29b). White crystals:
mp 149 ꢁC (n-hexane/AcOEt); IR (KBr) 3528, 1717, 1651 cmꢀ1; EIMS
m/z 431 (Mþ), 413, 276, 218; HRMS m/z calcd for C22H25NO6S:
(270 MHz, CDCl3)
d
7.72 (d, J¼8.2 Hz, 2H), 7.36 (d, J¼8.2 Hz, 2H), 7.00
(dd, J¼15.5, 7.5 Hz,1H), 6.81 (d, J¼8.2 Hz,1H), 6.59 (dd, J¼8.2,1.6 Hz,
1H), 6.53 (d, J¼1.6 Hz, 1H), 5.67 (dd, J¼15.5, 1.3 Hz, 1H), 5.06 (d,
J¼6.2 Hz, 1H), 4.84 (d, J¼6.2 Hz, 1H), 4.01 (ddd, J¼8.5, 7.3, 6.9 Hz,
1H), 3.87 (s, 3H), 3.85 (s, 3H), 3.69 (s, 3H), 3.31 (dd, J¼11.5, 6.6 Hz,
1H), 3.07e2.96 (m, 2H), 2.47 (s, 3H); 13C NMR (68 MHz, CDCl3)
431.1403, found 431.1426; 1H NMR (400 MHz, CDCl3)
d 7.69 (d,
J¼8.3 Hz, 2H), 7.32 (d, J¼8.3 Hz, 2H), 7.09 (d, J¼8.3 Hz, 1H), 7.06 (dd,
J¼15.6, 4.9 Hz, 1H), 6.83 (d, J¼2.9 Hz, 1H), 6.80 (dd, J¼8.3, 2.9 Hz, 1H),
5.50 (d, J¼15.6 Hz, 1H), 4.61 (d, J¼15.2 Hz, 1H), 4.15e4.08 (m, 1H),
4.02e3.96 (m, 1H), 3.91 (d, J¼15.2 Hz, 1H), 3.82 (s, 3H), 3.67 (s, 3H),
3.11 (d, J¼12.7 Hz, 1H), 2.48 (d, J¼10.3 Hz, 1H), 2.44 (s, 3H); 13C NMR
d
166.42 (C), 149.31 (C), 148.62 (C), 147.15 (CH), 144.35 (C), 134.07
(C), 129.80 (CHꢂ2), 129.76 (C), 127.83 (CHꢂ2), 122.39 (CH), 120.14
(CH), 111.59 (CH), 110.93 (CH), 80.79 (CH2), 79.60 (CH), 55.86 (CH3),
55.83 (CH3), 51.47 (CH3), 51.19 (CH), 49.93 (CH2), 21.54 (CH3).
(100 MHz, CDCl3)
d 166.49 (C), 159.31 (C), 146.50 (CH), 143.82 (C),
137.94 (C), 135.92 (C), 134.00 (CH), 129.93 (CHꢂ2), 127.12 (CHꢂ2),
127.04 (C), 122.92 (CH), 116.02 (CH), 113.31 (CH), 69.15 (CH), 55.38
(CH3), 54.14 (CH), 53.80 (CH2), 53.25 (CH2), 51.62 (CH3), 21.52 (CH3).
Anal. Calcd for C22H25NO6S: C, 61.24; H, 5.84; N, 3.25. Found: C, 61.20;
H, 5.91; N, 3.19.
4.3.8. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-7,8-dimethoxy-2-tosyl-
2,3,4,5-tetrahydro-1H-2-benzazepin-5-yl]-propenoate (29c). White
needles: mp 99e100 ꢁC (n-hexane/AcOEt); IR (KBr) 3506, 1719,
1653 cmꢀ1; EIMS m/z 461 (Mþ), 443, 429, 306; HRMS m/z calcd for
C23H27NO7S: 461.1507, found 461.1535; 1H NMR (400 MHz, CDCl3)
d
7.69 (d, J¼8.3 Hz, 2H), 7.32 (d, J¼8.3 Hz, 2H), 7.04 (dd, J¼15.6,
4.3.4. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-6-methoxy-2-tosyl-2,3,4,5-
tetrahydro-1H-2-benzazepin-5-yl]-propenoate (30b). White crystals:
mp 201 ꢁC (MeOH); IR (ATR) 3504, 2922, 1705, 1586 cmꢀ1; MS
(SIMSþ) m/z 432 (MþHþ), 414, 382, 316; HRMS m/z calcd for
C22H26NO6S: 432.1479, found 432.1471; 1H NMR (270 MHz, CDCl3)
4.6 Hz, 1H), 6.79 (s, 3H), 6.68 (s, 3H), 5.50 (dd, J¼15.6, 2.2 Hz, 1H),
4.60 (dd, J¼14.9, 1.4 Hz, 1H), 4.19e4.10 (m, 1H), 4.00e3.92 (m, 2H),
3.91 (s, 3H), 3.87 (d, J¼14.9 Hz,1H), 3.86 (s, 3H), 3.67 (s, 3H), 3.09 (d,
J¼13.9 Hz, 1H), 2.54 (d, J¼8.3 Hz, 1H), 2.44 (s, 3H); 13C NMR
(68 MHz, CDCl3)
d 166.47 (C), 148.55 (C), 148.11 (C), 146.07 (CH),
d
7.69 (d, J¼8.3 Hz, 2H), 7.31 (d, J¼8.3 Hz, 2H), 7.25 (t, J¼7.9 Hz, 1H),
143.82 (C), 135.83 (C), 129.94 (CHꢂ2), 129.07 (C), 127.45 (C), 127.07
(CHꢂ2), 122.94 (CH), 116.11 (CH), 113.41 (CH), 68.99 (CH), 56.08
(CH3), 56.00 (CH3), 54.80 (CH), 53.46 (CH2), 53.20 (CH2), 51.64
(CH3), 21.51 (CH3). Anal. Calcd for C23H27NO7S: C, 59.85; H, 5.90; N,
3.03. Found: C, 59.62; H, 6.05; N, 2.93.
7.01 (dd, J¼15.8, 4.3 Hz, 1H), 6.93 (d, J¼7.9 Hz, 1H), 6.90 (d, J¼7.9 Hz,
1H), 5.41 (dd, J¼15.8, 2.6 Hz,1H), 5.06e4.98 (m, 1H), 4.61 (dd, J¼14.8,
2.0 Hz, 1H), 4.28e4.19 (m, 1H), 3.99 (br d, J¼12.8 Hz, 1H), 3.83 (d,
J¼10.2 Hz, 1H), 3.80 (s, 3H), 3.65 (s, 3H), 3.09 (d, J¼12.8 Hz, 1H), 2.44
(d, J¼9.9 Hz, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 166.61 (C),
159.12 (C), 146.29 (CH), 143.76 (C), 138.70 (C), 135.92 (C), 129.93
(CHꢂ2), 129.11 (CH), 127.11 (CHꢂ2), 123.45 (C), 122.34 (CH), 121.84
(CH), 111.13 (CH), 68.65 (CH), 56.16 (CH3), 53.75 (CH2), 53.56 (CH2),
51.54 (CH3), 44.12 (CH2), 21.52 (CH3).
4.3.9. Methyl (2E,4SR)-4-(1,3-benzodioxol-5-yl-methyl)-4-[(5RS)-3-
tosyloxazolidin-5-yl]-2-butenoate (28d). Amorphous: IR (neat)
1734, 1655, 1350 cmꢀ1; EIMS m/z 445 (Mþ), 415, 342, 290; HRMS
m/z calcd for C22H23NO7S: 445.1194, found 445.1218; 1H NMR
(270 MHz, CDCl3)
d
7.72 (d, J¼8.2 Hz, 2H), 7.37 (d, J¼8.5 Hz, 2H), 6.95
4.3.5. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-7-methoxy-2-tosyl-2,3,4,5-
tetrahydro-1H-2-benzazepin-5-yl]-propenoate (31b). Amorphous: IR
(ATR) 3473, 2922, 1703, 1584 cmꢀ1; MS (SIMSþ) m/z 432 (MþHþ),
400, 369, 278; HRMS m/z calcd for C22H26NO6S: 432.1479, found
(dd, J¼15.8, 7.2 Hz, 1H), 6.74 (d, J¼7.2 Hz, 1H), 6.50 (s, 1H), 6.48 (d,
J¼7.2 Hz, 1H), 5.96 (s, 2H), 5.64 (dd, J¼15.8, 1.3 Hz, 1H), 5.06 (d,
J¼6.2 Hz, 1H), 4.83 (d, J¼6.3 Hz, 1H), 3.98 (ddd, J¼8.6, 7.3, 6.6 Hz,
1H), 3.68 (s, 3H), 3.32 (dd, J¼11.5, 6.6 Hz, 1H), 2.98 (dd, J¼11.5,
7.3 Hz, 1H), 2.95 (dd, J¼8.6, 7.3 Hz, 1H), 2.48 (s, 3H); 13C NMR
432.1473; 1H NMR (400 MHz, CDCl3)
d
7.69 (d, J¼8.2 Hz, 2H), 7.32 (d,
J¼8.2 Hz, 2H), 7.21 (d, J¼8.3 Hz, 1H), 7.21 (d, J¼8.3 Hz, 1H), 7.05 (dd,
J¼15.8, 4.9 Hz, 1H), 6.78 (d, J¼8.3 Hz, 1H), 6.74 (d, J¼2.4 Hz, 1H), 5.53
(dd, J¼15.8, 2.4Hz,1H), 4.64 (dd, J¼14.6,1.4 Hz,1H), 4.01e3.96 (m,1H),
3.93 (d, J¼14.2 Hz, 1H), 3.88 (d, J¼14.6Hz,1H), 3.79(s, 3H), 3.68 (s, 3H),
3.12 (dd, J¼14.2, 1.4 Hz, 1H), 2.56 (d, J¼10.3 Hz, 1H), 2.44 (s, 3H); 13C
(68 MHz, CDCl3) d 166.38 (C), 148.17 (C), 147.17 (C), 147.04 (CH),
144.43 (C), 134.02 (C), 130.94 (C), 129.87 (CHꢂ2), 127.86 (CHꢂ2),
122.46 (CH), 121.30 (CH), 108.76 (CH), 108.05 (CH), 101.22 (CH2),
80.83 (CH2), 79.53 (CH), 51.51 (CH3), 51.25 (CH), 49.96 (CH2), 21.55
(CH3).
NMR (100 MHz, CDCl3) d 166.40 (C),159.64 (C),145.73 (CH),143.74 (C),
137.08 (C), 135.96 (C), 131.25 (CH), 129.90 (CHꢂ2), 128.67 (C), 127.08
(CHꢂ2),123.14 (CH),118.86 (CH),112.40 (CH), 69.34 (CH), 55.28 (CH3),
54.98 (CH), 53.08 (CH2), 52.96 (CH2), 51.62 (CH3), 21.50 (CH3).
4.3.10. Methyl (2E)-3-[(4SR,5RS)-4-hydroxy-7,8-methylenedioxy-2-
tosyl-2,3,4,5-tetrahydro-1H-2-benzazepin-5-yl]-propenoate
(29d). Amorphous; IR (ATR) 3493, 2900,1718 cmꢀ1; MS (FABþ) m/z