Highly stereoselective protonation of the enolate of a bicyclic cycloheptatrienyl lactone occurs on the hindered face

Org Lett. 2002 Jun 13;4(12):2059-61. doi: 10.1021/ol025905r.

Abstract

[reaction: see text] The H/D exchange of the lactone-fused cycloheptatriene 1 is over 1000 times faster than that of the epimer 2. Interconversion of 1 and 2 provides an equilibrium mixture of 1:0.7, showing a similar stability of the isomers. Protonation of the common enolate 7 occurs far more readily on the more hindered face. Cycloheptatrienide anion is bent and as stable as a divinylcarbanion.