Selective Boryl‐Anion Migration in a Vinyl sp2−sp3 Diborane Induced by Soft Borane Lewis Acids

An intramolecular 1,2‐boryl‐anion migration from boron to carbon has been achieved by selective activation of the π system in (vinyl)B₂Pin₂)]^? using “soft” BR₃ electrophiles (BR₃=BPh₃ or 9‐aryl‐BBN). The soft character is key to ensure 1,2‐migration proceeds instead of oxygen coordination/B?O activation. The BR₃‐induced 1,2‐boryl‐anion migration represents a triple borylation of a vinyl Grignard reagent using only B₂Pin₂ and BR₃ and forms differentially protected 1,1,2‐triborylated alkanes. Notably, by increasing the steric bulk at the β position of the vinyl Grignard reagent used to activate B₂Pin₂, 1,2‐boryl‐anion migration can be suppressed in favor of intermolecular {BPin}^? transfer to BPh₃, thus enabling simple access to unsymmetrical sp²?sp³ diboranes.