Abstract

AbstractOrganoboron 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.

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