Controlling olefin geometry with Pd catalysis: selective formation of Z-olefins from both E- and Z-allylic carbonates.

The palladium-catalyzed formation of Z-olefins from allylic carbonates and a variety of protected dialkyl aminomalonates is reported. The reaction is selective for the Z-isomer, and either acetyl, Boc, or formyl protecting groups are tolerated. The Z-olefin product can be formed regardless of whether the E- or Z-allylic carbonate is used as starting material.