UNUSUAL BASE-INDUCED REARRANGEMENT OF EXO-9-OXABICYCLO[4.2.1]NON-7-ENE OXIDE TO EXO-8-HYDROXYBICYCLO[3.3.O]OCTAN-2-ONE

摘要

Reaction of exo-9-oxabicyclo[4.2.1]non-7-ene oxide with n-BuLi gives exo-8-hydroxybicyclo[3.3.0]octan-2-one. Potential reaction pathways for this unusual rearrangement were evaluated with the aid of computational studies. The process is proposed to proceed by elimination to a transient allene oxide, which rearranges to a trans-epoxide enolate before undergoing epoxide α-lithiation and transannular C-H insertion.