Metal-Free, DTBP-Mediated Methylthiolation of Arylboronic Acids with Dimethyldisulfide

Abstract

An efficient method for the C–S bond formation via the coupling reaction of arylboronic acids with dimethyldisulfide has been developed under the metal-free conditions. This novel protocol provides an attractive route for the synthesis of aryl methyl sulfides, due to its operational simplicity, satisfactory yields, excellent functional-group tolerance, as well as the mild reaction conditions.

Key words

methylthiolation - arylboronic acids - dimethyldisulfide - aryl methyl sulfides - di-tert-butyl peroxide

• References and Notes

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• 22 General Procedure Arylboronic acid (1.0 mmol), dimethyldisulfide (2.0 mmol), DTBP (3.0 mmol), and MeCN (2.0 mL) were taken in a sealed tube. The reaction mixture was stirred at 120 °C for 12 h in air. After cooling to room temperature, the product was diluted with H₂O (5 mL) and extracted with EtOAc (4 × 10 mL). The extracts were combined and washed by brine (3 × 10 mL), dried over MgSO₄, filtered, and evaporated, and purified by chromatography on silica gel to obtain the desired products with EtOAc–hexane (1:30 to 1:100 v/v). The products were characterized by their spectral and analytical data and compared with those of the known compounds (see Supporting Information). Typical Data for Representative Compound 4-Methylthioanisole (Table 2, Entry 2) Colorless oil. ¹H NMR (300 MHz, CDCl₃): δ = 7.17–7.14 (d, J = 8.1 Hz, 2 H), 7.08–7.05 (d, J = 8.1 Hz, 2 H), 2.42 (s, 3 H), 2.28 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 135.0, 134.8, 129.7, 127.3, 20.9, 16.5. GC-MS (EI): m/z = 138 [M⁺].
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