Sequential Ni-catalyzed borylation and cross-coupling of aryl halides via in situ prepared neopentylglycolborane

A procedure for NiCl2(dppp)-catalyzed pinacolborylation and neopentylglycolborylation that utilizes in situ prepared inexpensive pinacolborane and neopentylglycolborane is reported. The scope of this reaction was demonstrated with a variety of aryl bromides and iodides. The resulting aryl neopentylglycolboronic esters undergo a NiCl2(dppe)-catalyzed cross-coupling with aryl halides, resulting in an extremely effici cost-effective method for the synthesis of functional biaryls, dendritic building blocks, and other complex architectures.