Formal Halogen Transfer of Bromoarenes via Stepwise Reactions.

Abstract

A two-step halogen transfer of bromoarenes is reported. Mono-, di-, and tribromoaryllithiums generated through deprotonative lithiation were converted into organozinc species by in situ zincation, which were then subjected to bromination to provide the corresponding di-, tri-, and tetrabromoarenes, respectively, in 41-95% yields. Regioselective bromine-magnesium exchange with ethylmagnesium chloride followed by electrophilic trapping afforded benzene, pyridine, quinoline, pyrimidine, and thiazole derivatives with the bromo group translocated from the original position in 28-86% yields.