September 2003
1073
ϩ
ϩ
d: 58.6 (C6-OMe), 64.4 (C6a), 66.8 (C3a), 67.5 (C8a), 92.6 (C6), 119.9, 165.9. MS (m/z): 424 (M ), 330 (M ϪOPh). Anal. Calcd for C H N O :
2
1
18
2
4
1
21.7, 125.3, 126.9, 128.6, 128.9, 129.2, 134.9, 135.0, 137.1, 153.6, 165.0.
C, 73.57; H, 4.75; N, 6.60. Found: C, 73.62; H, 4.62; N, 6.61%.
8db: Colorless prisms. mp 242—244 °C (from EtOH–acetone) IR (KBr)
ϩ
ϩ
MS (m/z): 362 (M ), 330 (M ϪOMe). Anal. Calcd for C H N O : C,
6
2
1
18
2
4
Ϫ1
1
9.60; H, 5.01; N, 7.73. Found: C, 69.37; H, 4.99; N, 7.80%.
cm : 1774 (CϭO), 1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 4.83 (1H,
3
7
ea: Colorless prisms. mp 231—232 °C (from EtOH–acetone). IR (KBr) td, Jϭ4.6, 1.3, C8a-H), 5.19 (1H, s, C6-H), 5.37 (1H, d, Jϭ4.6, C3a-H),
Ϫ1
1
cm : 1768 (CϭO), 1712 (CϭO). H-NMR (270 MHz; CDCl ) d: 1.40 (3H,
6.31 (1H, dd, Jϭ10.6, 4.6, C8-H), 6.69—6.74 (2H, m, aromatic H), 6.88—
s, C9a-Me), 1.75 (3H, s, C8-Me), 3.46 (3H, s, C7-OMe), 3.72 (1H, dd, 6.93 (1H, m, aromatic H), 7.05—7.49 (11H, m, aromatic H and C7-H),
Jϭ10.9, 8.2, C4a-H), 3.79 (1H, m, C7a-H), 4.22 (1H, d, Jϭ2.3, C7-H), 4.68
3
1
3
7.72—7.77 (2H, m, aromatic H). C-NMR (67.5 MHz; CDCl ) d: 64.6
3
(
1H, d, Jϭ10.9, C1a-H), 4.94 (1H, d, Jϭ8.2, C5a-H), 5.58 (1H, m, C9-H),
(C6a), 66.9 (C3a), 67.5 (C8a), 88.5 (C6), 115.8, 119.9, 122.3, 122.6, 125.4,
1
3
7
.20—7.26 (2H, aromatic H), 7.41—7.51 (3H, aromatic H). C-NMR 127.0, 128.7, 129.3, 129.4, 134.4, 137.0, 153.5, 156.7, 164.0. MS (m/z): 424
ϩ
ϩ
(
5
1
125 MHz; CDCl ) d: 19.3 (C8-Me), 27.2 (C9a-Me), 44.7 (C4a), 56.8 (C7a),
(M ), 330 (M ϪOPh). Anal. Calcd for C H N O : C, 73.57; H, 4.75; N,
3
21 18 2 4
7.0 (C1a), 57.1 (C7-OMe), 76.8 (C5a), 79.1 (C9a), 89.5 (C7), 125.7, 128.6, 6.60. Found: C, 73.30; H, 4.76; N, 6.49%.
ϩ
28.9, 129.3, 131.3, 134.3, 167.7, 171.9, 174.2. MS (m/z): 368 (M ), 353
7eb: Colorless prisms. mp 265—270 °C (from EtOH–acetone). IR (KBr)
ϩ
ϩ
Ϫ1
1
(
6
M ϪMe), 297 (M ϪMeOϪCϭCϭO). Anal. Calcd for C H N O : C, cm : 1768, 1710 (CϭO). H-NMR (400 MHz; CDCl ) d: 1.45 (3H, s, C9a-
2
0
20
2
5
3
5.21; H, 5.47; N, 7.60. Found: C, 64.80; H, 5.17; N, 7.60%.
fa: Colorless prisms. mp 176—177 °C (from EtOH). IR (KBr) cm
764 (CϭO), 1624 (CϭC). H-NMR (400 MHz; CDCl ) d: 1.45 (3H, s, d, Jϭ8.1, C5a-H), 5.62 (1H, m, C9-H), 7.02—7.08 (3H, aromatic H), 7.23—
3
13
Me), 1.74 (3H, s, C8-Me), 3.76 (1H, dd, Jϭ10.6, 8.1, C4a-H), 4.02 (1H, m,
C7a-H), 4.74 (1H, d, Jϭ10.6, C1a-H), 4.82 (1H, d, Jϭ2.2, C7-H), 4.96 (1H,
Ϫ1
7
:
1
1
C8a-Me), 1.76 (3H, d, Jϭ1.5, C7-Me), 2.28 (3H, d, Jϭ1.5, C2-Me), 3.26 7.50 (7H, aromatic H). C-NMR (125 MHz; CDCl ) d: 19.4 (C8-Me), 27.1
3
(
1H, m, C6a-H), 3.44 (3H, s, C6-OMe), 4.12 (1H, m, C6-Me), 5.02 (1H, m, (C9a-Me), 44.7 (C4a), 57.3 (C7a), 57.7 (C1a), 76.7 (C5a), 79.1 (C9a), 85.9
C3a-H), 5.32 (1H, m, C8-H), 7.52—7.63 (3H, aromatic H), 7.90—7.94 (2H, (C7), 116.2, 122.8, 125.6, 129.0, 129.3, 129.7, 131.2 (4), 133.9 (4), 157.0
1
3
ϩ
aromatic H). C-NMR (100 MHz; CDCl ) d: 14.4 (C7-Me), 18.7 (C8a-Me), (4), 167.1 (4), 171.9 (4), 174.2 (4). MS (m/z): 430 (M ), 297
3
ϩ
5
1
4.4 (C6a), 57.0 (C6-OMe), 58.1 (C3a), 82.5 (C8a), 88.3 (C6), 106.9, 124.4, (M ϪPhOϪCϭCϭO). Anal. Calcd. for C H N O : C, 69.76; H, 5.15; N,
27.3, 129.2, 133.0, 136.0, 141.7, 165.8, 167.6. MS (m/z): 376 (M ), 234 6.51. Found: C, 69.99; H, 5.08; N, 6.65%.
M ϪSO Ph). Anal. Calcd for C H NO S : C, 60.78; H, 5.64; N, 3.73.
Found: C, 60.32; H, 5.48; N, 3.76%.
2
5
22
2
5
ϩ
ϩ
Ϫ1
(
7fb: Colorless prisms. mp 182—183 °C (from EtOH). IR (KBr) cm :
2
19 21
5
1
1772 (CϭO), 1632 (CϭC), 1596 (CϭC), 1304, 1138 (–SO –). H-NMR
2
Reaction of 6b with 1a—c The reactions were performed according to (270 MHz; CDCl ) d: 1.49 (3H, s, C8a), 1.71 (3H, s, C7-Me), 2.29 (3H, d,
3
the general method using pheoxyacethylchloride.
Jϭ1.3, C2-Me), 3.20 (1H, m, C6a-H), 4.70 (1H, d, Jϭ2.0, C6-H), 5.15 (1H,
Ϫ1
7
ab: Colorless prisms. mp 155—158 °C. IR (KBr) cm : 1746 (CϭO), m, C3a-H), 5.35 (1H, m, C8-H), 7.02—7.09 (3H, aromatic H), 7.26—7.34
1
1
(
598 (CϭC). H-NMR (270 MHz; CDCl ) d: 1.69 (3H, s, C8a-Me), 1.87
(2H, aromatic H), 7.49—7.63 (3H, aromatic H), 7.91—7.94 (2H, aromatic
3
1
3
3H, m, C7-Me), 4.05 (1H, m, C6a-H), 4.93 (1H, d, Jϭ2.3, C6-H), 5.62 (1H, H). C-NMR (67.5MHz; CDCl ) d: 14.3 (C8a), 18.7 (C7), 26.9 (C2), 55.3
3
dd, Jϭ1.3, 1.7, C8-H), 5.88 (1H, s, C3a-H), 7.01—7.09 (3H, m, aromatic
(C6a), 58.3 (C3a), 82.2 (C8a), 84.8 (C6), 106.9, 116.2, 122.7, 124.9, 127.4,
ϩ
H), 7.19—7.39 (3H, m, aromatic H), 7.41—7.45 (2H, m, aromatic H),
129.2, 129.7, 133.1, 135.5, 141.7, 157.1, 164.9, 167.5. MS (m/z): 438 (M ),
1
3
ϩ
ϩ
7
.58—7.69 (2H, m, aromatic H). C-NMR (67.5 MHz; CDCl ) d: 18.5 (C7- 344 (M ϪOPh), 296 (M ϪSO Ph). Anal. Calcd for C H NO S: C, 65.89;
3
2 24 23 5
Me), 27.1 (C8a-Me), 55.6 (C6a), 66.6 (C3a), 73.8 (C8a), 85.3 (C6), 114.6, H, 5.30; N, 3.20. Found: C, 65.62; H, 5.25; N, 3.36%.
1
16.4, 120.3, 122.2, 123.1, 123.4, 124.6 (C8), 125.5, 129.1, 129.3, 129.6,
Reaction of 6c with 1a—c The reactions were performed according to
1
29.8, 134.8 (C6-OPh), 135.6 (N3-Ph), 152.8 (C7), 156.8 (C2), 165.9 (C5).
the general method uusing diphenylacetylchloride. Recrystallization from
ϩ
ϩ
ϩ
MS (m/z): 376 (M ), 333 (M ϪCO), 239 (M ϪCOϪOPh). HR-MS Calcd EtOH–acetone.
for C H N O (M ) m/z: 376.1423, Found: 376.1411.
ϩ
Ϫ1
22
20
2
4
7ac: Colorless prisms. mp 218—219 °C. IR (KBr) cm : 1758 (CϭO).
1
7
bb: Colorless prisms. mp 178—180 °C (from EtOH–acetone). IR (KBr)
H-NMR (270 MHz; CDCl ) d: 1.32 (3H, s, C8a-Me), 1.80 (3H, s, C7-Me),
3
Ϫ1
1
cm : 1766 (CϭO), 1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 1.73 (3H, 4.52 (1H, m, C6a-H), 5.55 (1H, m, C8-H), 6.06 (1H, s, C3a-H), 7.09—7.61
3
1
3
s, C8a-Me), 4.10 (1H, dd, Jϭ2.0, 1.3, C6a-H), 4.94 (1H, d, Jϭ2.0, C6-H), (15H, m, aromatic H). C-NMR (67.5 MHz; CDCl ) d: 18.9 (C7-Me), 26.8
3
6
.00 (2H, m, C3a-H, C8-H), 6.37 (1H, dd, Jϭ11.2, 1.3, C7-H), 6.94—7.07
(C8a-Me), 59.2 (C6a), 66.1 (C3a), 71.9 (C8a), 74.2 (C6), 120.0, 125.3,
(
3H, m, aromatic H), 7.20—7.44 (5H, m, aromatic H), 7.57—7.60 (2H, m,
125.6, 127.7, 127.9, 128.0, 128.1, 128.2, 128.8, 129.2, 134.9, 135.7, 136.2,
13
ϩ
aromatic H). C-NMR (67.5 MHz; CDCl ) d: 26.7 (C8a-Me), 52.9 (C6a), 137.8, 152.9, 171.2. MS (m/z): 436 (M ). Anal. Calcd for C H N O : C,
6
1
3
28 24
2
3
7.1 (C3a), 71.9 (C8a), 85.2 (C6), 115.4, 120.4, 122.9, 125.7, 126.1, 129.4, 77.04; H, 5.54; N, 6.42. Found: C, 76.75; H, 5.44; N, 6.38%.
ϩ
Ϫ1
29.7, 129.8, 135.4, 152.6, 156.6, 165.2. MS (m/z): 362 (M ), 318
7bc: Colorless prisms. mp 198—199 °C. IR (KBr) cm : 1738 (CϭO),
ϩ
1
(M ϪCO ). Anal. Calcd for C H N O : C, 69.60; H, 5.01; N, 7.73. Found:
1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 1.63 (3H, s, C8a-Me), 4.56
2
21 18
2
4
3
C, 69.54; H, 4.99; N, 7.76%.
(1H, dd, Jϭ2.0, 1.7, C6a-H), 5.68 (1H, dd, Jϭ10.9, 2.0, C7-H), 5.86 (1H,
7
cb: Colorless prisms. mp 165—166 °C (from EtOH–acetone). IR (KBr) dd, Jϭ10.9, 1.7, C8-H), 6.03 (1H, s, C3a-H), 7.15—7.40 (13H, m, aromatic
Ϫ1
1
13
cm : 1778 (CϭO), 1740 (CϭO), 1598 (CϭC). H-NMR (270 MHz; H), 7.59—7.62 (2H, m, aromatic H). C-NMR (67.5 MHz; CDCl ) d: 26.8
3
CDCl ) d: 2.18 (3H, t, Jϭ1.3, C7-Me), 5.30 (1H, dd, Jϭ8.6, 5.3, C8a-H), (C8a-Me), 56.1 (C6a), 67.5 (C3a), 72.4 (C8a), 73.1 (C6), 120.8, 125.9,
3
5
.36 (1H, s, C6-H), 6.13 (1H, dd, Jϭ5.3, 1.3, C8-H), 6.33 (1H, d, Jϭ8.6, 127.2, 127.8, 128.1, 128.2, 128.4, 128.8, 129.1, 129.2, 129.7, 135.9, 136.1,
13
ϩ
C3a-H), 6.98—7.46 (15H, aromatic H). C-NMR (67.5 MHz; CDCl ) d: 138.9, 153.2, 171.2. MS (m/z): 422 (M ).
3
Ϫ1
1
1
1
9.9 (C7-Me), 61.2 (C3a), 65.3 (C8a), 65.7 (C6a), 87.3 (C6), 116.5, 119.4,
20.7, 122.8, 124.6, 127.7, 127.9, 128.1, 128.5, 129.2, 133.6, 134.7, 143.3, (CϭO), 1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 1.47 (3H, s, C7-Me),
7cc: Colorless prisms. mp 217—219 °C. IR (KBr) cm : 3056, 1754
1
3
ϩ
ϩ
52.5, 156.6, 165.3. MS (m/z): 438 (M ), 345 (M ϪOPh), 301 5.30 (1H, dd, Jϭ8.6, 5.3, C8a-H), 5.98 (1H, d, Jϭ5.3, C8-H), 6.51 (1H, d,
ϩ
ϩ
(
M ϪOPhϪCO ), 259 (M ϪOPhϪCO ϪC H O). Anal. Calcd for Jϭ8.6, C3a-H), 6.62—6.80 (4H, m, aromatic H), 6.97—7.43 (16H, m, aro-
2
2
2
2
1
3
C H N O : C, 73.96; H, 5.06; N, 6.39. Found: C, 73.60; H, 4.94; N, 6.40%.
matic H). C-NMR (67.5 MHz; CDCl ) d: 21.6 (C7-Me), 60.3 (C3a), 66.1
3
2
7
22
2
4
Ϫ1
8
cb: Colorless prisms. mp 181—183 °C. IR (KBr) cm : 1776 (CϭO), (8a), 70.0 (C6a), 78.5 (C6), 119.2, 122.4, 124.6, 126.9, 127.3, 127.9, 128.0,
1
1
4
596 (CϭC). H-NMR (270 MHz; CDCl ) d: 2.09 (3H, t, Jϭ1.3, C7-Me), 128.1, 128.3, 128.9, 129.0, 129.4, 135.2, 135.5, 137.5, 137.9, 144.6, 152.8,
.87 (1H, dd, Jϭ5.3, 4.6, C8a-H), 5.23 (1H, s, C6-H), 5.38 (1H, d, Jϭ5.3, 170.4. MS (m/z): 498 (M ). Anal. Calcd for C H N O : C, 79.50; H, 5.26;
3
ϩ
3
3
26
2
4
C3a-H), 6.02 (1H, dd, Jϭ4.6, 1.3, C8-H), 6.80—7.68 (15H, aromatic H). N, 5.62. Found: C, 79.69; H, 5.38; N, 5.79%.
13
Ϫ1
C-NMR (67.5 MHz; CDCl ) d: 20.4 (C7-Me), 66.7 (C3a), 67.2 (C6a), 69.1
7dc: Colorless prisms. mp 231—233 °C. IR (KBr) cm : 1744 (CϭO),
3
1
(
1
(
C8a), 87.8 (C6), 116.7, 119.6, 120.1, 122.9, 125.1, 128.3, 128.4, 128.5,
28.8, 129.2, 129.6, 134.6, 137.2, 142.6, 153.5, 157.2,164.2. MS (m/z): 438
1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 5.08 (1H, dd, Jϭ8.6, 5.0, C8a-
3
H), 5.91 (1H, dd, Jϭ10.9, 5.0, C8-H), 6.57 (1H, d, Jϭ8.6, C3a-H), 6.76—
ϩ
ϩ
ϩ
13
M ), 345 (M ϪOPh), 301 (M ϪOPhϪCO ). Anal. Calcd for C H N O : 7.76 (21H, m, C7-H and aromatic H). C-NMR (67.5 MHz; CDCl ) d: 61.5
2
27 22
2
4
3
C, 73.96; H, 5.06; N, 6.39. Found: C, 73.67; H, 5.02; N, 6.37%.
db: Colorless prisms. mp 167—169 °C (from benzene). IR (KBr) cm
(C3a), 63.9 (C8a), 67.0 (C6), 78.2 (C6a), 118.9, 121.2, 124.9, 126.5, 126.9,
Ϫ1
7
:
127.6, 127.8, 127.9, 127.9, 128.1, 128.7, 129.3, 136.0, 136.2, 136.7, 137.0,
1
ϩ
1
5
4
782 (CϭO), 1748 (CϭO), 1598 (CϭC). H-NMR (270 MHz; CDCl ) d: 137.6, 152.9, 172.2. MS (m/z): 484 (M ). Anal. Calcd for C H N O :
3
32 24
2
3
.20 (1H, dd, Jϭ8.3, 4.6, C8a-H), 5.21 (1H, s, C6-H), 6.27 (1H, dd, Jϭ10.6, 79.32; H, 4.99; N, 5.78. Found: C, 79.26; H, 4.86; N, 5.86%.
Ϫ1
.6, C8-H), 6.49 (1H, d, Jϭ8.3, C3a-H), 6.65—6.69 (2H, m, C7-H and aro-
7ec: Colorless prisms. mp 264—266 °C. IR (KBr) cm : 1760, 1722
1
3
1
matic H), 6.89—7.51 (14H, m, aromatic H). C-NMR (67.5 MHz; CDCl3) (CϭO), 1596 (CϭC). H-NMR (270 MHz; CDCl ) d: 1.32 (3H, s, C9a-Me),
3
d: 61.7 (C3a), 63.5 (C8a), 77.2 (C6a), 88.3 (C6), 115.7, 119.9, 122.7, 123.5, 1.55 (3H, s, C8-Me), 3.69 (1H, dd, Jϭ10.9, 8.3, C4a-H), 4.53 (1H, s, C7a-
1
25.3, 126.9, 128.1, 128.3, 129.3, 129.5, 134.1, 134.4, 135.4, 144.8, 156.5,
H), 4.86 (2H, m, C1a, C5a-H), 5.48 (1H, s, C9-H), 7.11—7.49 (15H, m, aro-