Directed Regioselective Carbometallation of 1,2-Dialkyl-Substituted Cyclopropenes.

A regio- and diastereoselective copper-catalyzed carbomagnesiation of 1,2-dialkylated cyclopropenes is reported. The regioselectivity is controlled by a subtle tethered Lewis basic moiety. The chelating moieties allow the differentiation between two electronically tantamount organometallic intermediates. Further functionalization grants access to polysubstituted stereodefined cyclopropanes bearing up to five alkyl groups.