Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to allenes: efficient construction of tertiary and quaternary carbon centers.

A rhodium-catalyzed chemo- and regioselective intermolecular decarboxylative addition of β-ketoacids to terminal allenes is reported. Using a Rh(I)/DPPF system, tertiary and quaternary carbon centers were formed with exclusively branched selectivity under mild conditions. Preliminary mechanism studies support that the carbon-carbon bond formation precedes the decarboxylation and the reaction occurs in an outer-sphere mechanism.