The first catalytic enantioselective allylic substitution reaction with alkylboron compounds has been achieved. The reaction between alkyl-9-BBN reagents and primary allylic Chlorides proceeded With excellent gamma-selectivities and high enantioselectivities under catalysis. of a Cu(I)-DTBM-SEGPHOS system. The protocol produces terminal alkenes with an allylic stereogenic center branched With functionalized sp(3)-alkyl groups. The reaction with a gamma-silicon-substituted allyl chloride affords an efficient strategy for the enantioselective synthesis of functionalized alpha-stereogenic chiral allylsilanes.