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Title: Remote C–H Functionalization via Selective Hydrogen Atom Transfer
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  more » « less
Award ID(s):
1654656
PAR ID:
10058198
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Synthesis
Volume:
50
Issue:
08
ISSN:
0039-7881
Page Range / eLocation ID:
1569 to 1586
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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