Sequential Ni-Catalyzed Borylation and Cross-Coupling of Aryl Halides via in Situ Prepared Neopentylglycolborane

A procedure for NiCl(2)(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 NiCl(2)(dppe)-catalyzed cross-coupling with aryl halides, resulting in an extremely efficient and cost-effective method for the synthesis of functional biaryls, dendritic building blocks, and other complex architectures.