Light-Induced Gold-Catalyzed Hiyama Arylation: A Coupling Access to Biarylboronates

Organoboron compounds are versatile synthetic building blocks. We herein report a new strategy, a photochemical gold-catalyzed chemo-selective Hiyama arylation of B,Si bifunctionalized reagents with diazonium salts, which is orthogonal to common strategies and therefore a unique tool for synthesis of valuable biarylboronates. With this new methodology a wide array of diversely functionalized sp(2)- and sp(3)-hybridized biarylboronates were obtained. Notably, the synergism of gold catalysis with copper catalysis or palladium catalysis, allows for one-pot iterative C-X (heteroatom) and C-C couplings for the rapid assembly of several simple fragments to relatively complex molecules. Mechanistic studies indicated that photosensitizer-free conditions were superior to gold/Ru(bpy)(3)Cl-2 dual catalysis.