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Dual Electrocatalysis Enables Enantioselective Hydrocyanation of Conjugated Alkenes

submitted on 09.09.2019, 03:06 and posted on 10.09.2019, 15:58 by Lu Song, Niankai Fu, Brian G. Ernst, Wai-Hang Lee, Michael O. Frederick, Robert A. DiStasio Jr., Song Lin
Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, we address this long-standing synthetic problem using an electrocatalytic strategy. Electrochemistry allows for the seamless combination of two classic radical reactions—cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation—to accomplish highly enantioselective hydrocyanation without the need for stoichiometric oxidant. We harness electrochemistry’s unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis sheds light on the origin of enantioinduction, for which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions that direct the enantio-determining C–CN bond formation. This discovery demonstrates the power of electrochemistry in accessing new chemical space and providing solutions to pertinent challenges in synthetic chemistry.


An electrocatalytic approach to discovering new synthetic transformations

National Institute of General Medical Sciences

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Cornell University


United States

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