Recent Advances on Alkoxy Radicals-Mediated C(sp3)—H Bond Functionalization via 1,5-Hydrogen Atom Transfer

doi:10.6023/cjoc202307028

Abstract

Intramolecular hydrogen atom transfer (HAT) has proved to be an effective method to achieve the selective functionalization of remote C—H bonds. In this fascinating research area, alkoxy radicals have emerged as an important intermediate to participate in intramolecular hydrogen atom transfer reactions. In particular, the burgeoning visible-light photoredox catalysis has provided a new platform for O-radical directed remote functionalization of C(sp³)—H bonds. The progress on the different mechanisms of alkoxy radical generation and their applications in the intramolecular 1,5-HAT reactions for remote C(sp³)—H bond functionalization in the past five years are comprehensively summarized.

Key words: visible light photocatalysis, alkoxy radical, remote functionalization, 1,5-hydrogen atom transfer (1,5-HAT)

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Yanshuo Zhu, Hongyan Wang, Penghua Shu, Ke'na Zhang, Qilin Wang. Recent Advances on Alkoxy Radicals-Mediated C(sp³)—H Bond Functionalization via 1,5-Hydrogen Atom Transfer[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 1-17.

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Fig. & Tab. 28

Scheme 1. Barton reaction

Scheme 2. Traditional method for the generation of alkoxy radicals

Scheme 3. Primary methods for alkoxy radical generation

Scheme 4. δ?Selective functionalization of alkanols enabled by visible-light-induced ligand-to-metal charge transfer

Scheme 5. δ-C(sp3)—H amination of alcohols enabled by visible light and iron cooperative catalysis

Scheme 6. Visible-light-induced remote C(sp3)—H arylation of alcohols

Scheme 7. Visible-light-induced remote C(sp3)—H cyanation of alcohols

Scheme 8. Silver-catalyzed δ-selective C—C bond formation of alkanols

Scheme 9. Ag-catalyzed δ-regioselective heteroarylation of alcohols

Scheme 10. Remote C(sp3)—H dehydrogenative coupling reaction of alcohols

Scheme 11. Visible-light-induced remote C(sp3)—H allylations of alcohols

Scheme 12. Asymmetric alkylation of remote C(sp3)—H enabled by iridium and rhodium dual catalysis

Scheme 13. Visible-light-induced remote C(sp3)—H functionalization of alcohols

Scheme 14. Enantioselective cyanation of remote C(sp3)—H via cooperative photoredox and copper catalysis

Scheme 15. Visible-light-induced remote C(sp3)—H alkynylation reaction of alcohols

Scheme 16. δ-Regioselective mono- and dihalogenation of alcohols

Scheme 17. Construction of δ-alkenols through radical C(sp3)—H Heck-type reaction

Scheme 18. Concerted catalysis by iron and light

Scheme 16. Visible-light-induced pyridylation of C(sp3)—H bonds

Scheme 20. Visible-light-induced remote C(sp3)—H functionalization of alcohols

Scheme 21. Metal-free alcohol-directed regioselective heteroarylation of remote C(sp3)—H bonds

Scheme 22. Visible-light-induced remote C(sp3)—H heteroarylation of alcohols

Scheme 23. Alcohol etherification enabled by visible-light photoredox catalysis

Scheme 24. Visible light‐induced intramolecular C—O bond formation

Scheme 25. Visible light‐induced distal construction of a C—SCF2R bond on alcohols

Scheme 26. Remote C(sp3)—H multi-functionalization of alcohols

Scheme 27. Fenton-inspired C(sp3)—H thioetherification reaction

Scheme 28. Alkoxy radicals-mediated remote functionalization

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烷氧自由基引发1,5-氢原子转移实现C(sp³)—H键官能团化的研究进展

Recent Advances on Alkoxy Radicals-Mediated C(sp³)—H Bond Functionalization via 1,5-Hydrogen Atom Transfer

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Fig. & Tab. 28

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