Catalytic Borylation using an Air‐Stable Zinc Boryl Reagent: Systematic Access to Elusive Acylboranes

The use of borylzinc reagents in palladium‐catalyzed borylation chemistry is described (i.e. a boron analogue of the Negishi coupling), including a one‐pot bench‐top protocol using an air‐ and moisture‐stable bis(boryl)zinc reagent. The steric/electronic properties of the boryl fragment employed enable a systematic method for accessing acylboranes, a rare class of organoboron species with great potential in chemical synthesis. The reactions proceed under mild conditions, use inexpensive commercial sources of palladium, and demonstrate a remarkable functional‐group tolerance.