8272
S.-S. P. Chou et al. / Tetrahedron 63 (2007) 8267–8273
J¼6.5, 17.0 Hz), 2.16–2.00 (1H, m); 13C NMR (CDCl3,
75 MHz) d 164.1, 151.1, 135.3, 129.9, 129.8, 128.4, 125.1,
124.0, 115.3, 51.3, 42.5, 34.0, 31.1; EIMS (relative inten-
sity) m/z 257 (M+, 100), 176 (42), 148 (25), 147 (14), 67
(31); HRMS m/z 257.0869 (calcd for C15H15NOS:
257.0874).
Acknowledgements
Financial support of this work by the National Science
Council of the Republic of China is gratefully acknowledged
(NSC 94-2113-M-030-005).
References and notes
4.5.2. 2-(Phenylthio)-1,6,7,10,10a-pentahydropyrido[1,2-
a]azepin-4-one (7b). Light yellow liquid. IR (film) 3057,
3018, 2929, 2894, 2830, 1643, 1593, 1462, 1423, 1367,
1. Rubiralta, M.; Giralt, E.; Diez, E. Structure, Preparation,
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1
1300, 1115, 985, 852, 752, 692 cmꢀ1; H NMR (CDCl3,
300 MHz) d 7.52–7.38 (5H, m), 5.78–5.58 (2H, m), 5.37
(1H, s), 4.16 (1H, ddd, J¼4.2, 5.4, 13.8 Hz), 3.91–
3.82 (1H, m), 3.26 (1H, ddd, J¼3.0, 10.1, 13.8 Hz), 2.70–
2.53 (2H, m), 2.51–2.20 (4H, m); 13C NMR (CDCl3,
75 MHz) d 163.2, 151.3, 135.3, 130.4 (2ꢂ), 129.9, 128.7,
126.3, 115.7, 57.1, 43.5, 35.3, 33.5, 29.9; EIMS (relative
intensity) m/z 271 (M+, 100), 270 (85), 204 (25), 176 (20),
162 (28), 147 (14), 110 (15), 77 (15), 67 (49), 65 (17);
HRMS m/z 271.1036 (calcd for C16H17NOS: 271.1031).
4.5.3. 7-Methyl-2-(phenylthio)-1,6,9,9a-tetrahydroqui-
nolizin-4-one (7c). Light yellow liquid. IR (film) 3054,
2966, 2910, 1638, 1597, 1473, 1453, 1439, 1423, 1320,
1273, 1250, 849, 751, 691 cmꢀ1
;
1H NMR (CDCl3,
300 MHz) d 7.52–7.38 (5H, m), 5.50–5.40 (1H, m), 5.35
(1H, s), 4.39 (1H, d, J¼18.0 Hz), 3.75–3.61 (1H, m), 3.47
(1H, d, J¼18.0 Hz), 2.74 (1H, dd, J¼6.6, 17.1 Hz), 2.38 (1H,
dd, J¼6.6, 17.1 Hz), 2.33–2.23 (1H, m), 2.10–1.98 (1H,
m), 1.68 (3H, s); 13C NMR (CDCl3, 75 MHz) d 163.9,
151.0, 135.1, 131.9, 129.7, 129.6, 128.2, 118.0, 115.0,
50.9, 45.9, 33.76, 31.0, 20.3; FABMS (relative intensity)
m/z 271 (M+, 21), 270 (39), 268 (9), 204 (11), 96 (9), 94 (10);
HRMS m/z 271.1111 (calcd for C16H17NOS: 271.1031).
6. Hussenether, T.; Troschuetz, R. J. Heterocycl. Chem. 2004, 41,
857–865.
7. Cheng, Y.-X.; Dukat, M.; Dowd, M.; Fiedler, W.; Martin, B.;
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177–190.
4.5.4. 2-(Phenylthio)-1,6,9,10,10a-pentahydropyrido[1,2-
a]azepin-4-one (7d). Dark brown liquid. IR (film) 3021,
2931, 2839, 1639, 1595, 1458, 1419, 1362, 1292, 844,
1
752, 692 cmꢀ1; H NMR (CDCl3, 300 MHz) d 7.51–7.37
(5H, m), 5.83–5.68 (2H, m), 5.35 (1H, dd, J¼0.9, 3.6 Hz),
4.82 (1H, dd, J¼4.8, 16.5 Hz), 3.85 (1H, quintet,
J¼6.0 Hz), 3.44–3.35 (1H, m), 2.70 (1H, ddd, J¼1.5, 6.0,
16.8 Hz), 2.43–2.35 (2H, m), 2.24–2.11 (1H, m), 1.92–
1.82 (2H, m); 13C NMR (CDCl3, 75 MHz) d 163.1, 151.4,
135.2, 130.7, 129.8, 129.7, 128.6, 128.2, 115.3, 56.9, 43.0,
34.5, 31.2, 25.4; EIMS (relative intensity) m/z 271(M+,
100), 270 (85), 204 (25), 176 (20), 162 (28), 147 (14), 110
(15), 77 (15), 67 (49), 65 (17); HRMS m/z 271.1039 (calcd
for C16H17NOS: 271.1031).
8. (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413–4450;
(b) F€urstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012–3043;
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18–29; (d) Felpin, F. X.; Lebreton, J. Eur. J. Org. Chem.
2003, 3693–3712.
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Perron, J.; Joseph, B.; Merour, J.-Y. Tetrahedron 2004, 60,
10099–10109.
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2238.
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1217; (b) Gundermann, K. D.; Holtman, P. Angew. Chem., Int.
Ed. Engl. 1966, 5, 668.
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77, 1031–1032.
4.5.5. 8-Methyl-2-(phenylthio)-1,6,9,9a-tetrahydroqui-
nolizin-4-one (7e). Light yellow liquid. IR (film) 2927,
2856, 1632, 1592, 1457, 1437, 1417, 1328 cmꢀ1; 1H NMR
(CDCl3, 300 MHz) d 7.54–7.38 (5H, m), 5.41 (1H, br s),
5.34 (1H, s), 4.51 (1H, d, J¼18.0 Hz), 3.77–3.72 (1H, m),
3.77–3.52 (1H, m), 2.77 (1H, ddd, J¼1.2, 6.6, 17.1 Hz),
2.42–2.32 (2H, m), 1.92–1.81 (1H, m), 1.69 (3H, s); 13C
NMR (CDCl3, 75 MHz) d 164.1, 151.0, 135.3, 131.5,
129.8, 129.8, 128.3, 118.6, 115.3, 51.3, 42.4, 35.8, 33.9,
22.9; EIMS (relative intensity) m/z 271 (M+, 100), 270
(19), 256 (29), 204 (20), 176 (33), 147 (12), 94 (17), 67
(33); HRMS m/z 271.1024 (calcd for C16H17NOS:
271.1031).
15. (a) Bohlmann, F. Chem. Ber. 1958, 91, 2157–2167; (b) Sonnet,
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