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Electrochemical Nozaki–Hiyama–Kishi Coupling: Scope, Applications, and Mechanism

preprint
submitted on 20.03.2021, 04:33 and posted on 22.03.2021, 13:11 by Yang Gao, david hill, wei hao, Brendon J. McNicholas, julien Vantourout, Ryan Hadt, Sarah Reisman, Donna Blackmond, Phil Baran
One of the most oft-employed methods for C–C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki–Hiyama–Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.

Funding

NIGMS CCMF

National Institute of General Medical Sciences

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NSF Center for Synthetic Organic Electrochemistry

Directorate for Mathematical & Physical Sciences

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History

Email Address of Submitting Author

pbaran@scripps.edu

Institution

Scripps Research

Country

USA

ORCID For Submitting Author

0000-0001-9193-9053

Declaration of Conflict of Interest

none

Version Notes

version 1.0

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