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Enantioselective Construction of Quaternary All-Carbon Centers via Copper-Catalyzed Arylation of Tertiary Carbon-Centered Radicals

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posted on 22.01.2019 by Lianqian Wu, Fei Wang, Pinhong Chen, Guosheng Liu
An enantioselective copper-catalyzed arylation of tertiary carbon-centered radicals, leading to quaternary all-carbon stereocenters, has been developed herein. The tertiary carbon-centered radicals, including both benzylic and nonbenzylic radicals, were produced by the addition of trifluoromethyl radical to α-substituted acrylamides, and subsequently captured by chiral aryl copper­(II) species to give C–Ar bonds with excellent enantioselectivity. Importantly, an acylamidyl (CONHAr) group adjacent to the tertiary carbon radical is essential for the asymmetric radical coupling. The reaction itself features broad substrate scope, excellent functional group compatibility and mild conditions.