Journal Article

Electrochemically driven desaturation of carbonyl compounds

Pierre-Georges, Echeverria, Wilke, Henrik R, Baran, Phil S, Takahira Yusuke, Li, Jinjun, Delbrayelle Dominique, Vantourout, Julien C, Yao Zhen, Gnaim Samer

2021

Overview

Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access 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 (1–100 g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway.Excising hydrogen adjacent to a carbonyl group—one of the most basic and widely employed transformations in organic synthesis—is traditionally achieved using metals and/or stoichiometric oxidants. Now, it has been shown that an electrochemically driven approach removes such requirements, resulting in a more sustainable and easily scalable method with wide substrate scope.

• Publisher: Nature Publishing Group
• Subject: Arrays / Carbonyl compounds / Carbonyl groups / Carbonyls / Chemistry / Copper / Desaturation / Electrochemistry / Hydrogen atoms / Interrogation / Methods / NMR / Nuclear magnetic resonance / Oxidants / Oxidation / Oxidizing agents / Phosphates / Reagents / Redox reactions / Silanes / Substrates / Sustainability / Transition metals