Reversal of expected stereochemical outcome in the oppolzer reaction of a cyclic N-enoylsultam: Enantioselective synthesis and absolute configuration of antispermatogenic hexahydroindeno[1,2-c]pyridines

Tetrahedron Letters

Volumn 38, Issue 21, 1997, Pages 3691-3694

  Jump, Joseph M ^a,c   McPhail, Andrew T ^b   Cook, C Edgar ^a  

^a RTI INTERNATIONAL   (United States)

^b DUKE UNIVERSITY   (United States)

^c Hoechst Celanese Corporation   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTISPERMATOGENIC AGENT; INDENO[1,2 C]PYRIDINE DERIVATIVE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; IN VITRO STUDY; REACTION ANALYSIS; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 0030967656     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00714-4     Document Type: Article

References (7)

1. Suter, K.E.; Hodel, C.; Gradient, F. Experientia 1977, 30, 810.
2. Cook, C.E.; Wani, M.C.; Jump, J.M.; Lee, Y.-W.; Fail, P.A.; Anderson, S.A.; Gu, Y.-Q.; Petrow, V. J. Med. Chem. 1995, 38, 753-763.
3. Oppolzer, W.; Poli, G.; Kingma, A. J.; Starkemann, C.; Bernardinelli, G. Helv. Chim. Acta 1987, 70, 2201-2214.
4. 3)].
5. 3).
6. min.(rel.) = 1.00:0.94] reflections with 1 > 3.0s(I). Atomic parameters, bond lengths, bond angles and torsion angles have been deposited at the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.
7. The ground state (GS) conformation of 4 undoubtedly has a twisted C=C-C=O conformation (see discussion in Kim, B.H.; Curran, D.P. Tetrahedron 1993, 49, 293-318). If the S-Oα and C=O are constrained to be syn by chelation with magnesium, a cisoid transition state would require that the aryl moiety be delivered from the top face of the molecule, probably by coordination of a second molecule of aryl Grignard with the amine nitrogen. A transoid transition state would allow the mechanism of Oppolzer (reference 4) to apply.