Pd/Cu Dual Catalyzed Asymmetric Synthesis of Highly Functional All‐Carbon Quaternary Stereocenters from Vinyl Carbonates

The challenging metal‐catalyzed asymmetric synthesis of highly functional quaternary carbon centers is reported using decarboxylative C(sp3)‒C(sp3) bond formation reactions. The key substrate, a vinyl cyclic carbonate, is activated to provide concomitantly both the requisite nucleophile (by formal umpolung) and electrophile reaction partner preceding the asymmetric crosscoupling process. A wide screening of reaction conditions, additives and catalyst precursors afforded a protocol that enabled access to a series of compounds featuring densely functionalized, elusive quaternary carbon stereocenters in appreciable yield and with enantiomeric ratios (er´s) of up to 90:10.