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Synlett 2019; 30(15): 1830-1834
DOI: 10.1055/s-0039-1690163
DOI: 10.1055/s-0039-1690163
letter
Molecular Iodine Catalyzed Hydroxysulfenylation of Alkenes with Disulfides in Aerobic Conditions
The authors gratefully acknowledge the National Natural Science Foundation of China (no. 21808085), the China Postdoctoral Science Foundation (2018M630519), and the Natural Science Foundation of Jiangsu Province, China (BK20160164).Further Information
Publication History
Received: 09 June 2019
Accepted after revision: 31 July 2019
Publication Date:
09 August 2019 (online)
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690163.
- Supporting Information
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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.