This paper describes a catalytic enantioselective route to synthesize functionalized all-carbon quaternary acyclic systems via a boron Lewis acid-promoted formal C-C insertion of diazoesters into aryl-CHO bonds. In the presence of chiral (S)-oxazaborolidinium cation Id as a catalyst, the reaction proceeded in good yield (up to 83%) with good regioselectivity (up to 88:12) and excellent enantioselectivity (up to 99% ee). The synthetic potential of this method was illustrated by conversion of the products to both alpha- and beta-amino esters.