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 using decarboxylative C(sp 3 )−C(sp 3 ) bond formation reactions is reported. 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 cross‐coupling process. A wide screening of reaction conditions, additives and catalyst precursors afforded a protocol that gave 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.