Dimethylcuprate-catalyzed decarboxylative coupling of allyl acetate

Abstract

Allylic alkylation of organocuprates represents an important class of C-C bond forming reactions. A drawback of these reactions is their stoichiometric nature. Although metal-catalyzed decarboxylative coupling reactions offer new opportunities for formation of C-C bonds, catalytic allylic alkylation reactions of organocuprates have not been previously reported. Here, multistage mass spectrometry experiments performed on ion trap mass spectrometers in conjunction with electronic structure calculations are used to demonstrate that the dimethylcuprate anion, [CH3CuCH3]-, can catalyze decarboxylative coupling of allyl acetate in the gas phase via a simple two-step catalytic cycle. In step 1, [CH..