Enantio- and Diastereoselective Cyclopropanation of 1-Alkenylboronates: Synthesis of 1-Boryl-2,3-Disubstituted Cyclopropanes

A novel, highly enantio- and diastereoselective synthesis of 1-boryl-2,3-disubstituted cyclopropanes has been developed by means of the cyclopropanation of alkenylboronates with ethyl diazoacetate in the presence of catalytic amounts of a chiral copper(I) complex. The products can also be directly accessed from alkynes through an operationally simple, sequential hydroboration-cyclopropanation protocol. The resulting enantioenriched 1-boryl-2,3-disubstituted cyclopropanes are versatile synthetic intermediates that undergo further transformations at the carbon-boron bond.