The rhodium(III)-catalyzed kinetic resolution of racemic nonactivated terminal alkene-tethered cyclohexadienones (1,6-dienes) has been developed with high to excellent selectivities (s up to 458) via asymmetric borylative cyclization, providing recovered cyclohexadienones and cis-hydrobenzofuranones with good to excellent yields and enantioselectivities (up to 99% ee). This reaction shows broad functional group tolerance and allows the further conversions of these two-type products to many optically active derivatives bearing multiple functionalities via Rh, Cu, Pd, and Ag catalysis.