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Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities
David C Miller1, Kyle T Tarantino1, Robert R Knowles2
1Department of Chemistry, Princeton University, Princeton, NJ, 08544, USA.
Topics in Current Chemistry (Cham)
|August 31, 2016
Summary
Proton-coupled electron transfers (PCETs) enable mild catalytic generation of organic radicals from common functional groups. This unconventional redox process offers a novel pathway for homolytic bond activation in organic synthesis.
Area of Science:
- Organic Chemistry
- Redox Chemistry
- Catalysis
Background:
- Proton-coupled electron transfer (PCET) involves simultaneous proton and electron transfer.
- PCET is crucial in biological redox catalysis and energy conversion.
- PCET applications in organic synthesis are emerging.
Purpose of the Study:
- To highlight the origins, development, and evolution of PCET processes for organic synthesis.
- To emphasize PCET's role in homolytic bond activation.
- To showcase PCET as a complementary mechanism to hydrogen atom transfer.
Main Methods:
- Review of literature on PCET in organic synthesis.
- Detailed description of PCET reactivity and mechanisms.
- Examples of PCET activation of organic functional groups.
Main Results:
- PCET provides a non-classical mechanism for homolytic bond activation.
- Enables direct generation of organic radical intermediates.
- Facilitates activation under mild catalytic conditions.
Conclusions:
- PCET offers synthetically advantageous reactivity for organic synthesis.
- PCET complements traditional hydrogen atom transfer methods.
- PCET facilitates the use of native functional group precursors.
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