Remote C–H Functionalization via Selective Hydrogen Atom Transfer

Abstract

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

Key words

hydrogen atom transfer - remote C–H functionalization - radicals - nitrogen-centered radicals - oxygen-centered radicals

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