Rapid Access to γ,γ‐Dichloroketones via Radical‐Induced Dichloromethylation and Concomitant 1,2‐Aryl Migration of Allylic Alcohols with CHCl3

Abstract A radical‐induced dichloromethylation and concomitant 1,2‐aryl migration of allylic alcohols with CHCl 3 is developed for the construction of γ,γ‐dichloroketones in moderate to good yields. We found that, for the para ‐substituted unsymmetrical substrates, the more electron‐deficient aryl group migrates preferentially over the more electron‐rich aryl group. Moreover, chlorocyclopropanes could be obtained from allyl alcohols in one‐pot manner through radical‐addition/1,2‐aryl migration/nucleophilic substitution.