articleScienceSep 1, 2016GREEN OA

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Shanghai Institute of Organic Chemistry · University of Chinese Academy of Sciences · +1 more institution

PubMed
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Abstract

Direct methods for stereoselective functionalization of sp 3 -hybridized carbon–hydrogen [C(sp 3 )–H] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp 3 )–CN bond formation upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric…

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