Oxidative Substitution of Organocopper(II) by a Carbon-Centered Radical.

J Am Chem Soc

State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China.

Published: August 2024

AI Article Synopsis

  • The study investigates the role of copper(II) species and alkyl radicals in copper-catalyzed coupling reactions of alkyl halides by exploring a new fluoroalkylcopper(III) complex using blue LED light.
  • The complex undergoes a process that generates Cu(II) and carbon-centered radicals, which then recombine to form a Cis isomer, shedding light on the mechanistic pathway.
  • Findings suggest that the interaction between organocopper(II) and carbon-centered radicals predominantly follows an "oxidative substitution" mechanism, relevant for copper-catalyzed C-H bond trifluoromethylation reactions.

Article Abstract

Copper-catalyzed coupling reactions of alkyl halides are believed to prominently involve copper(II) species and alkyl radicals as pivotal intermediates, with their exact interaction mechanism being the subject of considerable debate. In this study, a visible light-responsive fluoroalkylcopper(III) complex, [(terpy)Cu(CF)(CHCOBu)] , was designed to explore the mechanism. Upon exposure to blue LED irradiation, undergoes copper-carbon bond homolysis, generating Cu(II) species and carbon-centered radicals, where the carbon-centered radical then recombines with the Cu(II) intermediate, resulting in the formation of , the Cis isomer of . Beyond this, a well-defined fluoroalkylcopper(II) intermediate ligated with a sterically hindered ligand was isolated and underwent full characterization and electronic structure studies. The collective experimental, computational, and spectroscopic findings in this work strongly suggest that organocopper(II) engages with carbon-centered radicals via an "oxidative substitution" mechanism, which is likely the operational pathway for copper-catalyzed C-H bond trifluoromethylation reactions.

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Source
http://dx.doi.org/10.1021/jacs.4c07552DOI Listing

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