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

A radical-induced dichloromethylation and concomitant 1,2-aryl migration of allylic alcohols with CHCl3 is developed for the construction of gamma,gamma-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.

Automated summary

A method for constructing γ,γ-dichloroketones through CHCl3-induced radical-dichloromethylation and 1,2-aryl migration was developed. The more electron-deficient aryl group in para-substituted unsymmetrical substrates was found to migrate preferentially. Moreover, chlorocyclopropanes could be obtained from allylic alcohols through radical-addition/1,2-aryl migration/nucleophilic substitution in a one-pot manner.