Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities

David C. Miller, Kyle T. Tarantino, Robert R. Knowles

Research output: Contribution to journalReview articlepeer-review

113 Scopus citations


Proton-coupled electron transfers (PCETs) are unconventional redox processes in which both protons and electrons are exchanged, often in a concerted elementary step. While PCET is now recognized to play a central a role in biological redox catalysis and inorganic energy conversion technologies, its applications in organic synthesis are only beginning to be explored. In this chapter, we aim to highlight the origins, development, and evolution of the PCET processes most relevant to applications in organic synthesis. Particular emphasis is given to the ability of PCET to serve as a non-classical mechanism for homolytic bond activation that is complimentary to more traditional hydrogen atom transfer processes, enabling the direct generation of valuable organic radical intermediates directly from their native functional group precursors under comparatively mild catalytic conditions. The synthetically advantageous features of PCET reactivity are described in detail, along with examples from the literature describing the PCET activation of common organic functional groups.

Original languageEnglish (US)
Article number30
JournalTopics in Current Chemistry
Issue number3
StatePublished - Jun 1 2016

All Science Journal Classification (ASJC) codes

  • General Chemistry


  • Free radicals
  • Hydrogen atom transfer
  • Organic synthesis
  • Proton-coupled electron transfer


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