Catalytic Enantioselective Desymmetrization of COT-Monoepoxide. Maximum Deviation from Coplanarity for an S_N2‘-Cuprate Alkylation

Abstract

[reaction: see text] The first alkylative and enantioselective ring-opening of COT-monoepoxide (1) without the occurrence of any ring-contraction-isomerization by the use of in situ-formed organocuprates is reported. Because of the particular geometric constraint of compound 1, this work reports the largest deviation from coplanarity between the pi-orbital of the double bond and the sigma-bond connecting the leaving group ever observed for an S(N)2'-cuprate alkylation.