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The selective functionalization of remote C–H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis. This radical-mediated strategy provides access to novel reactivity that is complementary to closed-shell pathways. As modern methods for mild generation of radicals are continually developed, inherent selectivity paradigms of HAT mechanisms offer unparalleled opportunities for developing new strategies for C–H functionalization. This review outlines the history, recent advances, and mechanistic underpinnings of intramolecular HAT as a guide to addressing ongoing challenges in this arena. 1 Introduction 2 Nitrogen-Centered Radicals 2.1 sp3 N-Radical Initiation 2.2 sp2 N-Radical Initiation 3 Oxygen-Centered Radicals 3.1 Carbonyl Diradical Initiation 3.2 Alkoxy Radical Initiation 3.3 Non-alkoxy Radical Initiation 4 Carbon-Centered Radicals 4.1 sp2 C-Radical Initiation 4.2 sp3 C-Radical Initiation 5 Conclusion
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This content will become publicly available on January 2, 2026
Visible-light-driven net-1,2-hydrogen atom transfer of amidyl radicals to access β-amido ketone derivatives
Visible-light-driven N-centered radicals lead to C-centered α-amino radicals through rare net-1,2-HAT processes, with trapping by silyl enol ethers to access β-amido ketone derivatives.
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- Award ID(s):
- 2154593
- PAR ID:
- 10626728
- Publisher / Repository:
- RCS
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 16
- Issue:
- 2
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 962 to 969
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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