Pd(0)-Catalyzed Diastereoselective and Enantioselective Intermolecular Heck–Miyaura Borylation of Internal Enamides for the β-Aminoboronate Ester Synthesis

Miyaura borylation is widely recognized as one of the most reliable methods for constructing an organoboron compound. Reported herein is Pd(0)-catalyzed asymmetric three-component Heck–Miyaura borylation with the interception of internal olefin, aryldiazonium salt, and diboron reagent. This Heck-triggered borylation protocol proceeds in a highly chemoselective, diastereoselective, and enantioselective manner, thus allowing the expedient construction of 1,2-diaryl substituted β-aminoboronate esters derivatives with vicinal stereogenic centers. The versatility of the resulting benzylic boronic esters allows for their further transformation to more-intricate chiral amines.