Electrochemically driven desaturation of carbonyl compounds

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

Research output: Contribution to journalArticlepeer-review

Abstract

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. [Figure not available: see fulltext.]

Original languageEnglish
Pages (from-to)367-372
Number of pages6
JournalNature Chemistry
Volume13
Issue number4
DOIs
StatePublished - Apr 2021

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Chemical Engineering

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