We have developed an Ir-catalyzed asymmetric allylic alkylation via1,2-boron shift to access enantioenriched gem-diborylalkenes. In this reaction, excellent enantioselectivities were obtained by simply improving the reaction temperature via an impressive DKR process. DFT calculations and extensive mechanistic studies were conducted to elucidate the reaction mechanism and the origin of excellent enantioselectivities.