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. 2017 Jun 7;139(22):7448-7451.
doi: 10.1021/jacs.7b03539. Epub 2017 May 23.

Scalable, Electrochemical Oxidation of Unactivated C-H Bonds

Yu Kawamata  1 , Ming Yan  1 , Zhiqing Liu  2 , Deng-Hui Bao  2 , Jinshan Chen  3 , Jeremy T Starr  3 , Phil S Baran  1
Affiliations

Scalable, Electrochemical Oxidation of Unactivated C-H Bonds

Yu Kawamata et al. J Am Chem Soc. .

Abstract

A practical electrochemical oxidation of unactivated C-H bonds is presented. This reaction utilizes a simple redox mediator, quinuclidine, with inexpensive carbon and nickel electrodes to selectively functionalize "deep-seated" methylene and methine moieties. The process exhibits a broad scope and good functional group compatibility. The scalability, as illustrated by a 50 g scale oxidation of sclareolide, bodes well for immediate and widespread adoption.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A) The challenge of electrochemical C–H oxidation. (B) Reaction development and optimization. (C) Cyclic voltammograms of selected mediators.
Scheme 1
Scheme 1. Scope of the Quinuclidine-Mediated Electrochemical C–H Oxidation
Figure 2
Figure 2
(A) 50 g scale C–H oxidation of sclareolide enabled the synthesis of 2-oxo-yahazunone. (B) Putative mechanism for the quinuclidine-mediated electrochemical C–H oxidation.
See this image and copyright information in PMC

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