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Fenton-Inspired C-H Functionalization: Peroxide-Directed C-H Thioetherification.

ABSTRACT: Substoichiometric iron mediates the thioetherification of unactivated aliphatic C-H bonds directed by resident silylperoxides. Upon exposure to a catalytic amount of iron(II) triflate, TIPS-protected peroxides bearing primary, secondary, and tertiary C-H sites undergo chemoselective thioetherification of remote C-H bonds with diaryl disulfides. The reaction demonstrates a broad substrate scope and functional group tolerance without the use of any noble metal additives. Mechanistic experiments suggest that the reaction proceeds through 1,5-H atom abstraction by a hydroxyl radical generated with iron.

SUBMITTER: Groendyke BJ

PROVIDER: S-EPMC7423317 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Fenton-Inspired C-H Functionalization: Peroxide-Directed C-H Thioetherification.

Groendyke Brian J BJ Modak Atanu A Cook Silas P SP

The Journal of organic chemistry 20190916 20

Substoichiometric iron mediates the thioetherification of unactivated aliphatic C-H bonds directed by resident silylperoxides. Upon exposure to a catalytic amount of iron(II) triflate, TIPS-protected peroxides bearing primary, secondary, and tertiary C-H sites undergo chemoselective thioetherification of remote C-H bonds with diaryl disulfides. The reaction demonstrates a broad substrate scope and functional group tolerance without the use of any noble metal additives. Mechanistic experiments su ...[more]

PMID: 31524395

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