Recent Advances in Vinyl Radical-Mediated Hydrogen Atom Transfer

doi:10.6023/cjoc202108027

Abstract

In recent years, vinyl radical-mediated hydrogen atom transfer (HAT) has received increasing attention. This protocol provides an efficient pathway for radical cyclization and regioselective C(sp³)—H bond functionalization including vinylation, alkynylation, halogenation, arylation, etc. Generally, vinyl radicals are generated from single electron reduction of vinyl halides or the addition of extra radical to alkynes. The reaction pathways depend on substrates. For example, the resulting alkyl radical arising from vinyl radical-mediated HAT process is prone to be intramolecularly re-added to alkene, leading to cyclic products. When employing specific propargyl alcohols as substrates, the cyclic alkyl radical intermediate undergoes β-scission of C—C bond to realize vinyl migration. In addition, intermolecular radical trapping usually occurs by using internal alkynes. The transformation based on vinyl radical-mediated HAT features high regioselectivity, good atom-economy, and broad diversity of reaction modes. The recent advances in this research area are summarized.

Key words: radical reaction, C—H bond functionalization, 1,5-hydrogen atom transfer, functional group migration, vinyl radical

Cite this article

Baitong Yue, Xinxin Wu, Chen Zhu. Recent Advances in Vinyl Radical-Mediated Hydrogen Atom Transfer[J]. Chinese Journal of Organic Chemistry, 2022, 42(2): 458-470.

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Fig. & Tab. 21

Scheme 1. Three types of transformations involving vinyl radical-mediated HAT

Scheme 2. Vinyl radical-induced hydrosulfonylation of alkyne

Scheme 3. Vinyl radical-mediated cascade reaction for constructing fused ring

Scheme 4. Vinyl radical-mediated construction of 6(5)-6-5 fused ring

Scheme 5. Vinyl radical-mediated cascade reaction for constructing fused ring

Scheme 6. Vinyl radical-mediated cascade cyclization triggered by decarboxylation of aliphatic acids

Scheme 7. Vinyl radical-mediated cascade reaction for constructing [6.5.6] fused ring

Scheme 8. Vinyl radical-mediated cascade reaction for constructing cyclic sulfones

Scheme 9. Vinyl radical-mediated [4+2] cyclization

Scheme 10. Vinyl radical-mediated tri-functionalization of alkynes

Scheme 11. Vinyl radical-mediated regioselective vinylation of remote C(sp3)—H bonds

Scheme 12. Vinyl radical-mediated regioselective trifluoromethylthiolation of C(sp3)—H bond

Scheme 13. Regioselective sulfonylvinylation of the unactivated C(sp3)—H bond mediated by vinyl radical

Scheme 14. Sulfonylvinylation of C(sp3)—H bond enabled by ring-opening of cycloketone oxime

Scheme 15. Vinylation of C(sp3)—H bond involving alkanes

Scheme 16. Photocatalytic remote oxyfluoroalkylation of heteroalkynes via 1,5-HAT

Scheme 17. Vinyl radical-mediated remote trifluoromethyl- alkynylation of thioalkynes

Scheme 18. Vinyl radical-mediated remote fluoroalkyl-halogenation of thioalkynes

Scheme 19. Vinyl radical-mediated remote fluoroalkyl-halogenation of thioalkynes

Scheme 20. Vinyl radical-mediated arylation of C(sp3)—H bond

Scheme 21. Vinyl iodide-mediated radical cyclization

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