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Electrochemically Driven Desaturation of Carbonyl Compounds

preprint
submitted on 01.07.2020 and posted on 02.07.2020 by Samer Gnaim, Yusuke Takahira, Henrik Wilke, Zhen Yao, Jinjun Li, Dominique Delbrayelle, Pierre-Georges Echeverria, Julien Vantourout, Phil Baran

Electrochemical techniques have long been heralded for their innate sustainability as efficient methods for achieving redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity. To date, the most reliable methods for achieving it have relied on transition metals (Pd/Cu) or stoichiometric reagents based on I, Br, Se, or S. Herein we report an operationally simple pathway to such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1-100g), and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Mechanistic interrogation suggests a radical-based reaction pathway.

Funding

NIH Grant (GM-118176)

NSF (#1740656)

Fulbright Israel

Council for Higher Education VATAT

Yad Hanadiv

AGC Inc.

History

Email Address of Submitting Author

pbaran@scripps.edu

Institution

Scripps Research

Country

United States

ORCID For Submitting Author

0000-0001-9193-9053

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Version 1.0

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