Divergence between organometallic and single-electron-transfer mechanisms in copper(II)-mediated aerobic c-h oxidation

Alison M. Suess, Mehmed Z. Ertem, Chris Cramer, Shannon S. Stahl

Research output: Contribution to journalArticlepeer-review

337 Scopus citations

Abstract

Copper(II)-mediated C-H oxidation is the subject of extensive interest in synthetic chemistry, but the mechanisms of many of these reactions are poorly understood. Here, we observe different products from CuII-mediated oxidation of N-(8-quinolinyl)benzamide, depending on the reaction conditions. Under basic conditions, the benzamide group undergoes directed C-H methoxylation or chlorination. Under acidic conditions, the quinoline group undergoes nondirected chlorination. Experimental and computational mechanistic studies implicate an organometallic C-H activation/functionalization mechanism under the former conditions and a single-electron-transfer mechanism under the latter conditions. This rare observation of divergent, condition-dependent mechanisms for oxidation of a single substrate provides a valuable foundation for understanding CuII-mediated C-H oxidation reactions.

Original languageEnglish (US)
Pages (from-to)9797-9804
Number of pages8
JournalJournal of the American Chemical Society
Volume135
Issue number26
DOIs
StatePublished - Jul 3 2013

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