Catalytic Enantioselective Hydroboration of Cyclopropenes

2,2-Disubstituted cyclopropyl boronates have been synthesized with high degrees of diastereo- and enantioselectivity via the rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes. A strong directing effect of ester and alkoxymethyl substituents has been demonstrated. The directing effect was found to be necessary in achieving high degrees of enantiomeric induction. Selected cyclopropylboronic derivatives were successfully employed in the Suzuki cross-coupling reaction to produce the corresponding optically active aryl- and vinylcyclopropanes in good yields.