Molecular Iodine Catalyzed Hydroxysulfenylation of Alkenes with Disulfides in Aerobic Conditions

Abstract

An environmentally friendly and efficient strategy has been developed for preparing β-hydroxy sulfides by a molecular-iodine-catalyzed radical reaction. This reaction involves hydroxysulfenylation of alkenes with disulfides in aqueous solution. Air is used as the oxidant without any additives. Control experiments indicated that the oxygen atom of products might come from O₂. Both aryl alkenes and aliphatic alkenes were well tolerated in this transformation and afforded the corresponding products in moderate to high yields.

Key words

hydroxysulfenylation - hydroxy sulfides - iodine catalysis - green chemistry

• References and Notes

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• 13 β-Hydroxy Sulfides 3; General ProcedureA 20 mL reaction vessel equipped with a magnetic stirring bar was charged with the appropriate disulfide 1 (0.5 mmol), alkyne 2 (1 mmol), I₂ (20 mol%), and 1:1 MeCN–H₂O (2 mL), and the mixture was stirred under air at 60 °C for 2 h. Surplus I₂ was quenched with sat. aq Na₂S₂O₃, and the mixture was extracted with EtOAc (3 × 10 mL). The organic phases were combined, dried (Na₂SO₄), filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel, hexanes–EtOAc (4:1)].2-[(4-Chlorophenyl)thio]-1-(4-fluorophenyl)ethanol (3b)Colorless oil; yield: 101.5 mg (72%); ¹H NMR (400 MHz, CDCl₃): δ = 7.51–7.16 (m, 6 H), 7.10–7.04 (m, 2 H), 4.86–4.71 (m, 1 H), 3.50–3.09 (m, 2 H), 2.81–2.53 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 163.7, 161.3, 137.7, 133.4, 133.1, 131.7, 129.3, 127.53, 115.5, 71.2, 44.3. ¹⁹F NMR (376 MHz, CDCl₃): δ = –114.0. ESI-MS: m/z = 283 [M + 1]⁺. Anal. Calcd for C₁₄H₁₂ClFOS: C, 59.47; H, 4.28. Found: C, 59.30; H, 4.39.