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RSC Advances
110.2, 103.9, 61.2, 59.1, 26.2, 13.6; IR (cmꢁ1, neat): 3399, 3091,
2924, 2853, 1791, 1734, 1695, 1526, 749; LRMS (EI) m/z: 446.0;
HRMS (EI) calculated for C23H18N4O6 (M)+ 446.1226 found
446.1224; [a]2D5 ¼ ꢁ70ꢀ (c ¼ 0.001, CHCl3); HPLC analysis: (15%
i-PrOH/hexanes, 1 mL minꢁ1, 256 nm); 98% ee: tR ¼ 19.8 min.
(S)-Ethyl 2-(3,3-diphenylpropyl)-1-oxo-3-selenoxo-
1,2,3,7,12,12a-hexahydroimidazo [10,50:1,7]azepino[4,5-b]
indole-6-carboxylate (7i)
Brown solid, 0.079 g, 80%; mp 161–163 ꢀC; 1H NMR (400 MHz,
acetone-d6): d 10.80 (s, 1H), 8.98 (s, 1H), 7.62–7.56 (m, 2H),
7.41–7.38 (m, 4H), 7.34–7.27 (m, 4H), 7.21–7.14 (m, 3H), 7.09
(t, J ¼ 8.0 Hz, 1H), 4.47–4.34 (m, 2H), 4.31 (dd, J ¼ 10.9, 1.9 Hz,
1H), 4.18 (t, J ¼ 7.8 Hz, 1H), 4.11–3.98 (m, 2H), 3.77 (dd, J ¼
16.3, 2.0 Hz, 1H), 3.06 (dd, J ¼ 16.3, 10.9 Hz, 1H), 2.63–2.54
(m, 2H), 1.40 (t, J ¼ 7.1 Hz, 3H); 13C NMR (101 MHz, acetone-
d6): d 185.7, 170.9, 167.2, 144.3, 135.5, 133.6, 128.4, 127.6,
127.6, 127.0, 126.3, 122.6, 119.5, 117.7, 111.7, 110.6, 106.9,
61.4, 60.8, 49.0, 43.3, 13.6; IR (cmꢁ1, neat): 3400, 3058, 2960,
2918, 2850, 1750, 1699, 1609, 1381, 744, 700; LRMS (EI) m/z:
583.1; HRMS (EI) calculated for C32H29N3O3Se (M)+ 583.1374
found 583.1381; [a]D25 ¼ ꢁ35ꢀ (c ¼ 0.001, CHCl3); HPLC anal-
ysis: (15% i-PrOH/hexanes, 1 mL minꢁ1, 256 nm); 99% ee: tR ¼
39.7 min.
(S)-Ethyl 2-(4-nitrophenyl)-1-oxo-3-thioxo-1,2,3,7,12,12a-
hexahydroimidazo [10,50:1,7]azepino[4,5-b]indole-6-
carboxylate (7f)
Yellow solid, 0.086 g, 87%; mp 199–201 ꢀC; 1H NMR (300 MHz,
acetone-d6): d 10.85 (s, 1H), 8.99 (s, 1H), 8.47 (d, J ¼ 8.9 Hz, 2H),
7.86 (d, J ¼ 8.9 Hz, 2H), 7.64 (dd, J ¼ 11.7, 8.1 Hz, 2H), 7.21 (t, J ¼
7.4 Hz, 1H), 7.12 (t, J ¼ 7.4 Hz, 1H), 4.81 (d, J ¼ 10.7 Hz, 1H),
4.48–4.38 (m, 2H), 3.96 (d, J ¼ 16.3 Hz, 1H), 3.41 (dd, J ¼ 16.1,
10.7 Hz, 1H), 1.41 (t, J ¼ 7.1 Hz, 3H); 13C NMR (75 MHz, acetone-
d6): d 181.0, 170.1, 167.2, 148.0, 139.3, 135.5, 131.6, 130.1, 127.6,
127.1, 124.1, 122.7, 119.6, 117.7, 111.7, 110.9, 106.8, 61.4, 60.9,
26.2, 13.6; IR (cmꢁ1, neat): 3400, 3085, 2981, 2925, 2852, 1767,
1696, 1611, 1527, 1345, 1247, 745; LRMS (EI) m/z: 462.1; HRMS
(EI) calculated for C23H18N4O5S (M)+ 462.0998 found 462.0997;
[a]2D5 ¼ ꢁ75ꢀ (c ¼ 0.001, CHCl3); HPLC analysis: (15% i-PrOH/
hexanes, 1 mL minꢁ1, 256 nm); 98% ee: tR ¼ 23.0 min.
(S)-Ethyl 2-cyclopentyl-1,3-dioxo-1,2,3,7,12,12a-
hexahydroimidazo [10,50:1,7]azepino[4,5-b]indole-6-
carboxylate (7j)
(S)-Ethyl 1-oxo-2-propyl-3-thioxo-1,2,3,7,12,12a-
hexahydroimidazo [10,50:1,7] azepino[4,5-b]indole-6-
carboxylate (7g)
1
ꢀ
Pale yellow solid, 0.078 g, 79%; mp 151–153 C; H NMR (400
MHz, acetone-d6): d 10.79 (s, 1H), 8.93 (s, 1H), 7.61 (d, J ¼ 8.3 Hz,
1H), 7.57 (d, J ¼ 8.1 Hz, 1H), 7.17 (t, J ¼ 8.1 Hz, 1H), 7.09 (t, J ¼
8.0 Hz, 1H), 5.23–5.12 (m, 1H), 4.48 (dd, J ¼ 10.7, 1.8 Hz, 1H),
4.45–4.35 (m, 2H), 3.83 (dd, J ¼ 16.1, 2.0 Hz, 1H), 3.11 (dd, J ¼
16.1, 10.8 Hz, 1H), 2.27–2.12 (m, 2H), 2.02–1.85 (m, 4H), 1.73–
1.59 (m, 2H), 1.39 (t, J ¼ 7.1 Hz, 3H); 13C NMR (101 MHz,
acetone-d6): d 182.4, 182.4, 170.8, 167.3, 135.4, 132.5, 127.9,
127.0, 122.5, 119.4, 117.6, 111.6, 110.5, 105.8, 61.3, 59.9, 59.9,
56.4, 26.2, 25.1, 25.1, 13.6; IR (cmꢁ1, neat): 3401, 3085, 3057,
2956, 2925, 2870, 1753, 1694, 1610, 1403, 742; LRMS (EI) m/z:
393.1; HRMS (EI) calculated for C22H23N3O4 (M)+ 393.1689
found 393.1679; [a]2D5 ¼ ꢁ30ꢀ (c ¼ 0.001, CHCl3); HPLC analysis:
(15% i-PrOH/hexanes, 1 mL minꢁ1, 256 nm); 99% ee: tR ¼ 25.1
min.
1
ꢀ
Pale yellow solid, 0.089 g, 90%; mp 152–154 C; H NMR (300
MHz, acetone-d6): d 10.80 (s, 1H), 8.92 (s, 1H), 7.63–7.56 (m, 2H),
7.18 (t, J ¼ 7.4 Hz, 1H), 7.09 (t, J ¼ 7.4 Hz, 1H), 4.52 (d, J ¼ 10.7
Hz, 1H), 4.45–4.33 (m, 2H), 3.96–3.79 (m, 3H), 3.08 (dd, J ¼ 16.1,
10.8 Hz, 1H), 1.84–1.70 (m, 2H), 1.40 (t, J ¼ 7.1 Hz, 3H), 0.97 (t, J
¼ 7.4 Hz, 3H); 13C NMR (75 MHz, acetone-d6): d 181.9, 171.0,
167.3, 135.4, 132.0, 127.9, 127.0, 122.5, 119.5, 117.6, 111.6,
110.5, 105.7, 61.3, 60.1, 43.9, 26.2, 20.3, 13.6, 10.5; IR (cmꢁ1
,
neat): 3401, 3085, 2964, 2934, 1754, 1694, 1610, 1399, 742; LRMS
(EI) m/z: 383.2; HRMS (EI) calculated for C20H21N3O3S (M)+
383.1304 found 383.1302; [a]2D5 ¼ ꢁ45ꢀ (c ¼ 0.001, CHCl3); HPLC
analysis: (15% i-PrOH/hexanes, 1 mL minꢁ1, 256 nm); 99% ee:
tR ¼ 38.7 min.
(S)-Ethyl 2-benzyl-1-oxo-3-thioxo-1,2,3,7,12,12a-
hexahydroimidazo [10,50:1,7]azepino[4,5-b]indole-6-
(S)-Ethyl 2-methyl-1-oxo-3-thioxo-1,2,3,7,12,12a-
hexahydroimidazo [10,50:1,7]azepino[4,5-b]indole-6-
carboxylate (7h)
carboxylate (7k)
1
1
ꢀ
Yellow solid, 0.090 g, 91%; mp 200–202 ꢀC; H NMR (300 MHz, Pale yellow solid, 0.088 g, 89%; mp 155–157 C; H NMR (400
acetone-d6): d 10.82 (s, 1H), 8.93 (s, 1H), 7.64 (d, J ¼ 8.0 Hz, 1H), MHz, acetone-d6): d 10.79 (s, 1H), 8.94 (s, 1H), 7.61 (d, J ¼ 7.9 Hz,
7.59 (d, J ¼ 8.3 Hz, 1H) 7.48 (d, J ¼ 7.3 Hz, 2H), 7.40–7.30 (m, 1H), 7.57 (d, J ¼ 8.1 Hz, 1H), 7.17 (t, J ¼ 8.1 Hz, 1H), 7.08 (t, J ¼
3H), 7.18 (t, J ¼ 7.6 Hz, 1H), 7.10 (t, J ¼ 7.4 Hz, 1H), 5.17 (s, 2H), 8.0 Hz, 1H), 4.53 (dd, J ¼ 10.7, 1.8 Hz, 1H), 4.46–4.32 (m, 2H),
4.68 (d, J ¼ 10.6 Hz, 1H), 4.48–4.35 (m, 2H), 3.90 (d, J ¼ 16.0 Hz, 3.85 (dd, J ¼ 16.1, 1.9 Hz, 1H), 3.34 (s, 3H), 3.10 (dd, J ¼ 16.1,
1H), 3.16 (dd, J ¼ 16.1, 10.9 Hz, 1H), 1.40 (t, J ¼ 7.1 Hz, 3H); 13
C
10.7 Hz, 1H), 1.39 (t, J ¼ 7.1 Hz, 3H); 13C NMR (101 MHz,
NMR (75 MHz, CDCl3): d 180.6, 170.7, 167.8, 134.9, 132.0, 128.9, acetone-d6): d 182.3, 170.8, 167.3, 135.4, 131.9, 127.9, 127.0,
128.7, 128.3, 128.0, 126.8, 123.1, 119.9, 117.8, 111.3, 110.1, 122.5, 119.4, 117.6, 111.6, 110.5, 105.6, 61.3, 60.3, 26.1, 13.6; IR
106.5, 61.8, 60.3, 46.0, 27.2, 14.2; IR (cmꢁ1, neat): 3391, 3081, (cmꢁ1, neat): 3398, 3085, 2918, 2849, 1758, 1694, 1610, 1401,
2916, 2849, 1754, 1692, 1605, 1384, 741; LRMS (EI) m/z: 431.2; 743; LRMS (EI) m/z: 355.0; HRMS (EI) calculated for
HRMS (EI) calculated for C24H21N3O3S (M)+ 431.1304 found
C
18H17N3O3S (M)+ 355.0991 found 355.0994; [a]2D5 ¼ ꢁ10ꢀ (c ¼
431.1309; [a]2D5 ¼ ꢁ50ꢀ (c ¼ 0.001, CHCl3); HPLC analysis: (15% 0.001, CHCl3); HPLC analysis: (15% i-PrOH/hexanes, 1 mL
i-PrOH/hexanes, 1 mL minꢁ1, 256 nm); 97% ee: tR ¼ 43.4 min. minꢁ1, 256 nm); 99% ee: tR ¼ 28.9 min.
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RSC Adv., 2015, 5, 73169–73179 | 73177