Synfacts 2016; 12(08): 0855
DOI: 10.1055/s-0035-1562695
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart · New York

N-Hydroxyphthalimide-Catalyzed Electrochemical Allylic Oxidation

Benjamin List
Tim Gatzenmeier
Horn EJ, Rosen BR, Chen Y, Tang J, Chen K, Eastgate MD, Baran PS * The Scripps Research Institute, La Jolla and Bristol–Myers Squibb, New Brunswick, USA; Asymchem Life Science (Tianjin), P. R. of China
Scalable and Sustainable Electrochemical Allylic C–H Oxidation.

Nature 2016;
533: 77-81
Further Information

Publication History

Publication Date:
19 July 2016 (online)



The Baran group reports an electrochemical oxidation of allylic methylene groups to give unsaturated ketones with t-BuOOH as the terminal oxidant. Anodic oxidation of the N-hydroxyphthalimide catalyst (Cl4NHPI) is proposed to give an oxyl radical species. Upon abstraction of a hydrogen atom from the substrate, the resulting allylic radical is suggested to further react with a tert-butyl peroxyl radical to give the product after elimination of t-BuOH.



Atom-economical and sustainable methods for allylic oxidations on an industrial scale are rare and cumbersome. This report suggests a catalyst-controlled electrochemical approach and aims for a simple and chemoselective solution. Although the isolated yields remain moderate in some cases, the broad scope as well as the low cost and toxicity of the materials render this methodology an auspicious alternative for large-scale applications.