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.

Automated summary

The challenging metal-catalyzed asymmetric synthesis of highly functional quaternary carbon centers using decarboxylative C(sp(3))-C(sp(3)) bond formation reactions has been successfully reported in this study. By activating a key substrate, a vinyl cyclic carbonate, both the requisite nucleophile and electrophile reaction partner were provided for the asymmetric cross-coupling process. Through extensive screening of reaction conditions, additives and catalyst precursors, a protocol was developed that allowed 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.