Rate acceleration of anionic oxy-cope rearrangements induced by an additional unsaturation

Loïc Gentric (1) , Issam Hanna (1) , Alexandre Huboux (1) , Rachida Zaghdoudi (1)

1 DCSO - Laboratoire de synthèse organique

(Matrix Presented) In sharp contrast to their isopropyl counterparts, a variety of (Z)-isopropenyl tertiary bicyclo[2.2.2]octenols undergo facile anionic oxy-Cope rearrangements allowing the stereoselective incorporation of an isopropenyl group into polycyclic skeletons such as the tricyclic system of vinigrol, bicyclo[5.3.1]undecane, and cis-decalin frameworks. This rate acceleration is probably due to the stabilization of the transition state by the additional unsaturation on the terminal position.

Domaines: Chimie organique

Loïc Gentric, Issam Hanna, Alexandre Huboux, Rachida Zaghdoudi. Rate acceleration of anionic oxy-cope rearrangements induced by an additional unsaturation. Organic Letters, 2003, 5 (20), pp.3631-3634. ⟨10.1021/ol035283p⟩. ⟨hal-00954832⟩