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.