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. 2019 Oct 18;84(20):13073-13091.
doi: 10.1021/acs.joc.9b01979. Epub 2019 Sep 16.

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

Brian J Groendyke  1 , Atanu Modak  1 , Silas P Cook  1
Affiliations

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

Brian J Groendyke et al. J Org Chem. .

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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Bioactive molecules bearing a 1,4-oxy-thio motif.
Figure 2.
Figure 2.
Directed radical chemistry as a route to C(sp3)–H thioetherification.
Scheme 1.
Scheme 1.
Thioetherification of an Unactivated C–H Bond
Scheme 2.
Scheme 2.
Radical-Clock Experiments
See this image and copyright information in PMC

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