Proton-coupled electron transfer in the reduction of carbonyls using SmI2-H2O: Implications for the reductive coupling of acyl-type ketyl radicals with SmI2-H2O

Shicheng Shi, Roman Szostak, Michal Szostak

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14 Scopus citations

Abstract

Samarium diiodide-water (SmI2-H2O) reagents have emerged as some of the most practical systems enabling reduction and reductive cyclizations of ketyl radicals. Recently, this reaction manifold has been extended to acyl-type radicals generated from cyclic polar carboxylic acid derivatives. However, the relationship between the fundamental electron- and proton-transfer steps in the generation of ketyl-type radicals with SmI2-H2O remains unclear. An intriguing scenario involves an initial proton-coupled electron transfer (PCET) mechanism from SmI2-H2O to the carbonyl group. Herein, we calculate with high accuracy bond dissociation free energies (BDFE) for the O-H bond in ketyl radicals in 14 cyclic and acyclic ketone, ester, imide and amide substrates and in anthracene relevant to reductions with SmI2-H2O and quantitatively assess the feasibility of concerted PCET in the reduction of carbonyl groups using SmI2-H2O. Reduction potentials of all substrates have been calculated. The data argue against concerted PCET from SmI2-H2O to carbonyl substrates.

Original languageEnglish (US)
Pages (from-to)9151-9157
Number of pages7
JournalOrganic and Biomolecular Chemistry
Volume14
Issue number38
DOIs
StatePublished - Jan 1 2016

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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