A diastereo- and enantioselective rhodium(III)-catalyzed reductive cyclization of cyclohexadienone-tethered terminal alkenes and ()-1,2-disubstituted alkenes (1,6-dienes) is reported, providing -bicyclic products bearing three contiguous stereocenters with good yields and high diastereo- and enantioselectivities. The kinetic resolution of the racemic precursor is also achieved with good efficiency. Moreover, a subgram-scale experiment, several transformations of the cyclization product, and one-pot preparation of bridged polycyclic frameworks are presented.
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