Chemoselective and Stereoselective Allylation of Bis(alkenyl)boronates

Bis(alkenyl)boronates react with optically active Ir(π‐allyl) species in a process that involves allylation of the more substituted olefin and 1,2‐metalate shift of the less substituted olefin. The method constructs valuable enantioenriched tertiary allylic boronic esters with high chemoselectivity, enantioselectivity and diastereoselectivity. Allylic functionalization reactions transform the 1,3‐stereodiad to 1,5‐ and 1,6‐stereochemical relationships.