Highly Efficient Synthesis of Alkylboronate Esters via Cu(II)-Catalyzed Borylation of Unactivated Alkyl Bromides and Chlorides in Air

A copper(II)-catalyzed borylation of alkyl halides with bis(pinacolato)diboron (B 2 pin 2 ) has been developed, which can be carried out in air, providing a wide range of primary, secondary, and some tertiary alkylboronates in high yields. A variety of functional groups are tolerated and the protocol is also applicable to unactivated alkyl chlorides (including 1,1- and 1,2-dichlorides). Preliminary mechanistic investigations show that this borylation reaction involves one-electron processes.