Reaction of cyclohexanones imines with substituted nitroolefins. New synthesis of tetrahydroindole derivatives

Tetrahedron Letters

Volumn 40, Issue 22, 1999, Pages 4177-4180

  Sethy, Lim ^a   Jabin, Ivan ^a   Revial, Gilbert ^a  

^a EUROPEAN SPACE AGENCY   (France)

Author keywords

Imines; Indoles; Michael reactions; Regioselection

Indexed keywords

ALKENE; CYCLOHEXANONE DERIVATIVE; ENAMINE; IMINE; INDOLE DERIVATIVE;

ARTICLE; CYCLIZATION; IONIZATION; SYNTHESIS;

EID: 0033612169     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00708-X     Document Type: Article

References (19)

1. Grob C.A., Camenisch K. Helvetica Chimica Acta. 1953, 36, 49-58.
2. Grob C.A., Schad H.P. Helvetica Chimica Acta. 1955, 38, 1121-1127.
3. Gomez-Sanchez A., Mancera M., Rosado F., Bellanato J. J. Chem. Soc. Perkin I 1980, 1199-1205.
4. Meyer H. Liebigs Ann. Chem. 1981, 1534-1544.
5. 7
6. (a) Pfau M., Ribière C. J. Chem. Soc., Chem. Commun. 1970, 66-67.
7. (b) Pfau M., Ughetto-Monfrin J. Tetrahedron 1979; 35, 1899-1904 and references therein.
8. (c) Pfau, M.; Tomas, A.; Lim, S.; Revial, G. J. Org. Chem. 1995, 60, 1143-1147.
9. Pfau, M.; Revial, G.; Guingant, A.; d'Angelo, J. J. Am. Chem. Soc. 1985, 107, 273-274. Jabin, I.; Revial, G.; Melloul, K.; and Pfau, M. Tetrahedron: Asymm. 1997, 8, 1101-1109 and reference 1 included.
10. Pfau, M.; Revial, G.; Guingant, A.; D'Angelo, J. J. Am. Chem. Soc. 1985, 107, 273-274. Jabin, I.; Revial, G.; Melloul, K.; and Pfau, M. Tetrahedron: Asymm. 1997, 8, 1101-1109 and reference 1 included.
11. Cyclohexanones imines were obtained from the corresponding cyclohexanones and primary amines in toluene solution at reflux in a Dean Stark water separator for 24 h.
12. 3) δ 1.65 to 1.75 (m, 4H), 1.75 (d, J = 7 Hz, 3H), 2.02 (d, J = 0.7 Hz, 3H). 2.15 to 2.25 (m, 1H), 2.35 to 2.45 (m, 3H). 5.15 (q, J = 7 Hz, 1H).
13. Madsen, J.O.; Lawesson, S.-O. Bull. Soc. Chim. Belg. 1976, 85, 819-828.
14. 3) δ 50.03, 110.0, 117.3, 119.96, 120.03, 122.06. 125.73, 125.82, 126.33, 126.81 (2C), 127.27 (2C), 127.62, 128.66 (2C), 128.72 (2C), 135.43, 137.01, 137.10.
15. Nitroolefins and were prepared according to the method of Mc Murry: Melton, J.; Mc Murry, J.E. J. Org. Chem. 1975, 40, 2138-2139.
16. This tetrahydroindole derivative is a somewhat unstable oily compound accounting for the observed moderate yield.
17. Molecular sieves were used since by-products were observed in this case.
18. 6c
19. In both cases the unstable minor isomers could not be isolated. However, because of the very high similarity of their mass spectrum respectively with those of tetrahydroindoles 15 and 16, it is highly probable that these compounds are bicyclic adducts i and ii, arising from "normal" adducts, i.e. those which are formed by the attack on the more substituted α-carbon atom of imine 14. (formula presented)