A copper-catalyzed regio-and diastereoselective borylacylation of α,β-unsaturated esters with B 2 pin 2 and acyl fluorides has been developed to afford the β'-boryl-βketoesters with high anti-diastereoselectivity (up to > 99 : 1). Additionally, the borylcarbamoylation is possible by using isocyanates as electrophiles instead of acyl fluorides. Moreover, the enantioselective borylacylation and borylcarbamoylation are also achieved by judicious choice of a chiral phosphoramidite-ligated copper complex.