Understanding Chemoselectivity in Proton-Coupled Electron Transfer: A Kinetic Study of Amide and Thiol Activation

Guanqi Qiu, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

While the mechanistic understanding of proton-coupled electron transfer (PCET) has advanced significantly, few reports have sought to elucidate the factors that control chemoselectivity in these reactions. Here we present a kinetic study that provides a quantitative basis for understanding the chemoselectivity in competitive PCET activations of amides and thiols relevant to catalytic olefin hydroamidation reactions. These results demonstrate how the interplay between PCET rate constants, hydrogen-bonding equilibria, and rate-driving force relationships jointly determine PCET chemoselectivity under a given set of conditions. In turn, these findings predict reactivity trends in a model hydroamidation reaction, rationalize the selective activation of amide N-H bonds in the presence of much weaker thiol S-H bonds, and deliver strategies to improve the efficiencies of PCET reactions employing thiol co-catalysts.

Original languageEnglish (US)
Pages (from-to)16574-16578
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number42
DOIs
StatePublished - Oct 23 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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