TBHP-Mediated Oxidative Cross-Coupling of Disulfides with Ethers through a C(sp³)-H Thiolation Process

Abstract

A new tert-butyl hydroperoxide (TBHP)–mediated oxidative cross-coupling of disulfides with ethers is presented for the synthesis of etherified sulfides. This method is achieved by a C(sp³)-H thiolation strategy under metal-free conditions and provides a simple route to constructing the C-S bonds.

GRAPHICAL ABSTRACT

Keywords:

• Cross-coupling reaction
• 1,2-disulfides
• ethers
• oxidation
• TBHP

Notes

^a Reaction conditions: 1a (0.3 mmol), 2a (2 mL), [O], and additive for 12 h. TBHP is hydrous (70% in water solution).

^b 68% of 1a was recovered.

^c >90% of 1a was recovered.

^d 2a (20 equiv) in ⁿ BuOAc (2 mL).

^e 1a (3 mmol, 0.654 g) for 48 h.

^a Reaction conditions: 1 (0.3 mmol), 2 (2 mL), TBHP (2.0 equiv; 70% in water solution), and 4 Å MS (100) at 120 °C for 12 h.

^b For 48 h.

^c The ratio given in parentheses was determined by ¹H NMR analysis.

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