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. 2014 Aug 10;356(11-12):2719-2724.
doi: 10.1002/adsc.201400032.

Metal-Free Preparation of Cycloalkyl Aryl Sulfides via Di-tert-butyl Peroxide-Promoted Oxidative C(sp3)[BOND]H Bond Thiolation of Cycloalkanes

Jincan Zhao  1 , Hong Fang  1 , Jianlin Han  2 , Yi Pan  1 , Guigen Li  3
Affiliations

Metal-Free Preparation of Cycloalkyl Aryl Sulfides via Di-tert-butyl Peroxide-Promoted Oxidative C(sp3)[BOND]H Bond Thiolation of Cycloalkanes

Jincan Zhao et al. Adv Synth Catal. .

Abstract

A concise thiolation of C(sp3)-H bond of cycloalkanes with diaryl disulfides in the presence of oxidant of di-tert-butylperoxide (DTBP) has been developed. This reaction without using any of metal catalyst, tolerates varieties of disulfides and cycloalkanes substrates, giving good to excellent chemical yields, which provides a useful approach to cycloalkyl aryl sulfides from unactivated cycloalkanes.

Keywords: C(sp3)–H activation; cycloalkane; metal-free; oxidative; thiolation.

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Figures

Scheme 1
Scheme 1
C(sp3)–H bond functionalization.
Scheme 2
Scheme 2
Thiolation of cyclohexane with disulfides. Reaction conditions: 1 (0.5 mmol), cyclohexane (2 mL), DTBP (4.0 equiv), 120 °C, 24 h. Isolated yields based on 1.
Scheme 3
Scheme 3
Thiolation of cyclopentane with disulfides. Reaction conditions: 1 (0.5 mmol), cycloalkanes (2 mL), DTBP (4.0 equiv), 120 °C, 24 h. Isolated yields based on 1.
Scheme 4
Scheme 4
Investigation of the intramolecular competition reaction. Reaction conditions: 1o (0.5 mmol), cyclohexane (2 mL), DTBP (4.0 equiv), 120 °C, 24 h.
Scheme 5
Scheme 5
Investigation of the intermolecular competition reaction. Reaction conditions: 1l (0.25 mmol), 1b (0.25 mol), cyclohexane (2 mL), DTBP (8.0 equiv), 120 °C, 24 h.
Scheme 6
Scheme 6
Insights into the mechanism.
Scheme 7
Scheme 7
A possible reaction mechanism.
See this image and copyright information in PMC

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