Reactions of cyclohexanone enamines with α,β-unsaturated thioesters and selenoesters

Synlett

Volumn , Issue 1, 2000, Pages 119-121

  Byeon, Chang Ho ^a   Hart, David J ^a   Lai, Chin Shan ^a   Unch, James ^a  

^a OHIO STATE UNIVERSITY   (United States)

Author keywords

, unsaturated selenoester; , unsaturated thioester; Bicyclo 3.3.1 nonane 2,9 dione; Conjugate addition; Enamines

Indexed keywords

BICYCLO[3.3.1]NONANE 2,9 DIONE; CYCLOHEXANONE DERIVATIVE; THIOESTER; UNCLASSIFIED DRUG;

ARTICLE; BROMINATION; CARBON NUCLEAR MAGNETIC RESONANCE; MOLECULAR DYNAMICS; REACTION ANALYSIS; SYNTHESIS;

EID: 0033957211     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (30)

1. Stork, G.; Kretchmer, R. A.; Schlessinger, R. H. J. Am. Chem. Soc. 1968, 90, 1647.
2. Barta, N. S.; Brode, A.; Stille, J. R. J. Am. Chem. Soc. 1994, 116, 6201.
3. Stork, G.; Terrell, R.; Szumszkovicz, J. J. Am. Chem. Soc. 1954, 76, 2029. Stork, G.; Landesman, H. J. Am. Chem. Soc. 1956, 78, 5128.
4. Stork, G.; Terrell, R.; Szumszkovicz, J. J. Am. Chem. Soc. 1954, 76, 2029. Stork, G.; Landesman, H. J. Am. Chem. Soc. 1956, 78, 5128.
5. Nelson, R. P.; Lawton, R. G. J. Am. Chem. Soc. 1966, 88, 3884. Nelson, R. P.; McEuen, J. M.; Lawton, R. G. J. Org. Chem. 1969, 34, 1225.
6. Nelson, R. P.; Lawton, R. G. J. Am. Chem. Soc. 1966, 88, 3884. Nelson, R. P.; McEuen, J. M.; Lawton, R. G. J. Org. Chem. 1969, 34, 1225.
7. Anzeveno, P. B.; Matthews, D. P.; Barhey, C. L.; Barbuch, R. J. J. Org. Chem. 1984, 49, 3134.
8. Gravel, D.; Rahal, S. Can. J. Chem. 1975, 53, 2671. Seebach, E.; Missbach, M.; Calderari, G.; Eberle, M. J. Am. Chem. Soc. 1990, 112, 7625.
9. Gravel, D.; Rahal, S. Can. J. Chem. 1975, 53, 2671. Seebach, E.; Missbach, M.; Calderari, G.; Eberle, M. J. Am. Chem. Soc. 1990, 112, 7625.
10. Hickmott, P. Proc. Chem. Soc. 1964, 287.
11. Harding, K. E.; Clement, B. A.; Moreno, L.; Peter-Katalinic, J. J. Org. Chem. 1981, 46, 940.
12. Butkus, E.; Stoncius, A. Synlett 1999, 234.
13. Hart, D. J.; Lai, C.-S. Synlett 1989, 49. Guevel, A.-C; Hart, D. J. Synlett 1994, 169.
14. Hart, D. J.; Lai, C.-S. Synlett 1989, 49. Guevel, A.-C; Hart, D. J. Synlett 1994, 169.
15. Stork, G.; Brizzolara, A.; Landesman, H.; Szumszkovicz, J.; Terrell, R. J. Am. Chem. Soc. 1963, 85, 207.
16. For the preparation of thioesters and selenoesters 2a and 2d see: Byeon, C-H.; Chen, C-Y.; Ellis, D. A.; Hart, D. J.; Li, J. Synlett 1998, 596. Micheal acceptors 2b and 2c (mp 90-91°C for X = SPh and 79-81°C for X = SePh) were prepared from the corresponding acid chlorides and PhSH or PhSeH in the presence of pyridine.
17. Marquet, A.; Jacques, J. Tetrahedron Lett. 1959, 1 (9), 24. Jacques, J.; Marquet, A. Org. Syn. Coll. Vol. 1988, 6, 175. The stereochemistry of bromide 6 is secure based on NMR experiments, but the stereochemistry of 5 (a single isomer) is uncertain.
18. Marquet, A.; Jacques, J. Tetrahedron Lett. 1959, 1 (9), 24. Jacques, J.; Marquet, A. Org. Syn. Coll. Vol. 1988, 6, 175. The stereochemistry of bromide 6 is secure based on NMR experiments, but the stereochemistry of 5 (a single isomer) is uncertain.
19. House, H. O.; Bashe, R. W. II J. Org. Chem. 1965, 30, 2942.
20. 8 the stereochemical course of these reactions have not been rigorously established with the exception of entry 12. For literature examples of reactions shown in entries 3, 6, 9, and 12, respectively, see: Hickmott, P. W.; Miles, G. J.; Sheppard, G.; Urbani, R.; Yoxall, C. T. J. Chem. Soc., Perkin 1 1973, 1514. Gelin, R.; Gelin, S.; Dolmazon, R. Bull Chim. Soc. Fr. 1973, 1409. Hickmott, P. W.; Hargreaves, J. R. Tetrahedron 1967, 23, 3151. Butkus, E.; Bielinyte, B. J. Prakt. Chem. 1992, 334, 285.
21. 8 the stereochemical course of these reactions have not been rigorously established with the exception of entry 12. For literature examples of reactions shown in entries 3, 6, 9, and 12, respectively, see: Hickmott, P. W.; Miles, G. J.; Sheppard, G.; Urbani, R.; Yoxall, C. T. J. Chem. Soc., Perkin 1 1973, 1514. Gelin, R.; Gelin, S.; Dolmazon, R. Bull Chim. Soc. Fr. 1973, 1409. Hickmott, P. W.; Hargreaves, J. R. Tetrahedron 1967, 23, 3151. Butkus, E.; Bielinyte, B. J. Prakt. Chem. 1992, 334, 285.
22. 8 the stereochemical course of these reactions have not been rigorously established with the exception of entry 12. For literature examples of reactions shown in entries 3, 6, 9, and 12, respectively, see: Hickmott, P. W.; Miles, G. J.; Sheppard, G.; Urbani, R.; Yoxall, C. T. J. Chem. Soc., Perkin 1 1973, 1514. Gelin, R.; Gelin, S.; Dolmazon, R. Bull Chim. Soc. Fr. 1973, 1409. Hickmott, P. W.; Hargreaves, J. R. Tetrahedron 1967, 23, 3151. Butkus, E.; Bielinyte, B. J. Prakt. Chem. 1992, 334, 285.
23. 8 the stereochemical course of these reactions have not been rigorously established with the exception of entry 12. For literature examples of reactions shown in entries 3, 6, 9, and 12, respectively, see: Hickmott, P. W.; Miles, G. J.; Sheppard, G.; Urbani, R.; Yoxall, C. T. J. Chem. Soc., Perkin 1 1973, 1514. Gelin, R.; Gelin, S.; Dolmazon, R. Bull Chim. Soc. Fr. 1973, 1409. Hickmott, P. W.; Hargreaves, J. R. Tetrahedron 1967, 23, 3151. Butkus, E.; Bielinyte, B. J. Prakt. Chem. 1992, 334, 285.
24. 3) of the mixture.
25. The morpholine enamine of cyclohexanone was used in enamine-acid chloride annulations.
26. This reaction sequence was applied to products from entries 1-3, 7-9, and 10-12. Melting points for all solid products (3/4) and intermediate enones (7) follow:3c (52-56°C), 3d (68-69°C), 4c (111-112°C), 4d (66-68°C), 7a (54-55°C), 7c (98-99°C).
27. 3) for all products (3/4) and intermediate enones (7) follow:3a:18.5 (t), 23.1 (q), 29.8 (d), 34.8 (t), 35.2 (t), 48.2 (t), 53.2 (d), 62.5 (d), 209.4 (s), 211.9 (s); 4a:18.1 (q), 20.1 (t), 28.4 (t), 28.5 (d), 34.4 (t), 47.6 (t), 50.7 (d), 65.4 (d), 208.5 (s), 211.3 (s); 3b:18.1 (t), 18.9 (q), 33.2 (d), 35.1 (t), 36.6 (t), 40.3 (d), 44.3 (t), 49.8 (d), 61.3 (d), 210.3 (s), 213.3 (s); 4b:20.3 (t), 20.6 (q), 20.9 (q), 28.5 (t), 30.7 (d), 34.5 (t), 40.4 (d), 45.4 (t), 47.4 (d), 65.5 (d), 208.7 (s), 211.5 (s); 3c: 18.2 (t), 35.1 (t), 35.9 (t), 40.8 (d), 49.2 (t), 53.8 (d), 61.8 (d), 126.6 (d), 127.0 (d), 129.1 (d), 144.7 (s), 208.6 (s), 212.1 (s); 4c:20.3 (t), 29.1 (t), 34.8 (t), 39.5 (d), 44.2 (t), 52.1 (d), 65.6 (d), 127.4 (d), 127.5 (d), 128.9 (d), 138.9 (s), 207.9 (s), 210.9 (s); 3d:18.7 (t), 35.4 (t), 35.6 (t), 40.6 (d), 42.0 (t), 48.0 (d), 52.6 (q), 63.2 (d), 173.3 (s), 207.2 (s), 209.4 (s); 4d:19.7 (t), 31.5 (t), 35.0 (t), 39.1 (d), 41.1 (t), 47.2 (d), 52.5 (q), 65.6 (d), 171.8 (s), 206.6 (s), 209.6 (s); 7a:18.9 (t), 22.5 (q), 29.6 (t), 32.6 (t), 54.4 (d), 61.4 (d), 130.0 (d), 159.8 (s), 197.7 (s), 208.1 (s); 7c: 17.0 (t), 30.9 (t), 33.1 (t), 51.6 (d), 61.7 (d), 126.7 (d), 127.9 (d), 129.2 (d), 130.9 (d), 135.7 (s), 157.0 (s), 197.9 (s), 208.2 (s); 7d: 16.6 (t), 30.5 (t), 33.7 (t), 48.7 (d), 53.0 (q), 62.6 (d), 135.8, (d), 145.9 (s), 164.9 (s), 198.6 (s), 206.9 (s).
28. It has been suggested that the C-acylation/conjugate addition mechanism is in part operative in the Hickmott annulation: Butkus, E. P.; Belinite-Vil'yams, B.; Purvanetskas, G.-E. V. Russ. J. Org. Chem. 1995, 31, 960. Butkus, E.; Bielinyte-Williams, B. Collect. Czech. Chem. Commun. 1995, 60, 1314. There is some disagreement in the literature on this point (see first article cited under reference 15).
29. It has been suggested that the C-acylation/conjugate addition mechanism is in part operative in the Hickmott annulation: Butkus, E. P.; Belinite-Vil'yams, B.; Purvanetskas, G.-E. V. Russ. J. Org. Chem. 1995, 31, 960. Butkus, E.; Bielinyte-Williams, B. Collect. Czech. Chem. Commun. 1995, 60, 1314. There is some disagreement in the literature on this point (see first article cited under reference 15).
30. These have all been suggested as possibilities for the Hickmott annulation.