Facile Approach for C(sp³)–H Bond Thioetherification of Isochroman

Abstract

An unprecedented C–S formation protocol via the direct oxidative C(sp³)–H bond thioesterification of isochroman under metal-free conditions was developed. A series of isochroman derivatives could be afforded efficiently by the green, simple, and atom-economical method.

Key words

C–S coupling - thioetherification - peroxides - dehydrogenation - isochroman

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• 16 General Procedure for the Oxidative C–S Formation A sealed tube was charged with isochroman (or benzylic ether; 1 mmol), DTBP (1.5 mmol), thiol (or thiophenol; 1.5 mmol). The reaction mixture was stirred at 120 °C for 6 h. The reaction mixture was then cooled to obtain a brown liquid. The organic solutions could be purified directly by column chromatography on silica gel to give the pure product (hexane–EtOAc, 20:1). 1-[(4-Chlorophenyl)thio]isochromane 3a Colorless oil; yield: 212 mg (77%). ¹H NMR (500 MHz, CDCl₃): δ = 7.56 (d, J = 8.3 Hz, 2 H), 7.40–7.30 (m, 3 H), 7.28–7.21 (m, 2 H), 7.20–7.11 (m, 1 H), 6.49 (s, 1 H), 4.55 (td, J = 11.5, 3.3 Hz, 1 H), 4.03 (dd, J = 11.3, 6.2 Hz, 1 H), 3.20–3.09 (m, 1 H), 2.72 (dd, J = 16.5, 2.4 Hz, 1 H). ¹³C NMR (126 MHz, CDCl₃): δ = 133.56, 132.90, 132.48, 132.27, 131.64, 128.06, 127.89, 126.93, 126.13, 125.16, 85.06, 76.39, 76.14, 75.89, 57.36, 26.75. Anal. Calcd for C₁₅H₁₃ClOS: C, 65.09; H, 4.73. Found: C, 64.88; H, 4.64. ESI-MS: m/z = 276.