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 sp2‐ and sp3‐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)3Cl2 dual catalysis. Organoboron compounds are versatile synthetic building blocks. A new strategy, namely a photochemical gold‐catalyzed chemoselective Hiyama arylation of B,Si bimetallic reagents with diazonium salts, which is orthogonal to common strategies and therefore a unique tool for synthesis of valuable biarylboronates, has been developed. With this new methodology a wide array of diversely functionalized sp2‐ and sp3‐hybridized biarylboronates were obtained.