Pd/Cu Dual‐Catalyzed Asymmetric Synthesis of Highly Functional All‐Carbon Quaternary Stereocenters from Vinyl Carbonates
Sijing Xue, Alexander Lücht, Jordi Benet‐Buchholz, Arjan W. Kleij
Abstract
Abstract 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.