Facile C–S Bond Cleavage of Aryl Sulfoxides Promoted by Brønsted Acid

Dedicated with respect and admiration to Prof. Barry M. Trost, a founding member of Science of Synthesis, on the occasion of the 20th anniversary of Science of Synthesis.

‡ These authors contributed equally to this work

Abstract

A method for the Brønsted acid promoted desulfination of aryl sulfoxides is presented. In the presence of a thiol, electron-rich sulfoxides undergo C–S bond cleavage to give the corresponding protodesulfinated arenes and disulfides.

Key words

sulfoxides - protodesulfination - deprotection - acid

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• 16 Protodesulfination; General Procedure To a solution of the sulfoxide (0.2 mmol, 1.0 equiv) and 1-octanethiol (0.8 mmol, 4.0 equiv) in CH₂Cl₂ (0.2 M) in a vial, trifluoromethanesulfonic acid (0.1 mmol, 0.5 equiv) was added and the mixture was stirred for 12 h at 23 °C. The reaction was quenched by the addition of solid NaHCO₃, stirred at 23 °C for 10 min, filtered and extracted with CH₂Cl₂. The resulting organic phase was dried over MgSO₄ and concentrated under reduced pressure to give a crude product that was purified by column chromatography (heptane/ethyl acetate).
• 17 1,3,5-Trimethoxy-2-(methylsulfinyl)benzene (1b) IR (neat): 2943, 1582, 1465, 1458, 1436, 1412, 1340, 1230, 1208, 1187, 1162, 1125, 1086, 1026 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 6.12 (s, 2 H), 3.88 (s, 6 H), 3.84 (s, 3 H), 3.04 (s, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 164.7, 161.3, 111.5, 91.3, 56.3, 55.7, 38.0. HRMS (ESI+): m/z [M + Na]⁺ calcd for C₁₀H₁₄O₄SNa: 253.0505; found: 253.0512.