Sodium Iodide Mediated Oxysulfenylation of Olefins with Thiosulfates: A Strategy for Constructing Sulfenylated 2,3-Dihydrobenzofurans and β-Acetoxy Sulfides

Abstract

A strategy has been developed for constructing sulfenylated 2,3-dihydrobenzofurans and β-acetoxy sulfides through NaI/DMSO-­mediated oxysulfenylation of alkenes with environmentally friendly thiosulfates. The reactions involve simple operations and give a series of sulfenylated 2,3-dihydrobenzofurans or β-acetoxy sulfides in moderate to good yields.

Key words

oxysulfenylation - alkenes - thiosulfates - dihydrobenzo­furans - acetoxy sulfides

• References and Notes

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• 13 2,3-Dihydro-1-benzofurans 3; General Procedure NaI (0.06 mmol) and the appropriate thiosulfate 2 (0.36 mmol) were added to a solution of 2-allylphenol (1a; 0.30 mmol) in MeCN (1 mL). DMSO (0.60 mmol) was then added and the mixture was stirred in a sealed tube at 100 °C for 3 h. When the reaction was complete, the mixture was diluted with EtOAc (3 × 5 mL) and the reaction was quenched with sat. aq Na₂SO₃. The mixture was extracted with EtOAc (3 × 10 mL), and the organic layers were combined, washed with H₂O (10 mL), dried (Na₂SO₄), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, PE). 2-[(Benzylthio)methyl]-2,3-dihydro-1-benzofuran (3a) Yellow oil; yield: 76.9 mg (91%). ¹H NMR (400 MHz, CDCl₃): δ = 7.34–7.25 (m, 5 H), 7.17–7.10 (m, 2 H), 6.87–6.79(m, 2 H), 4.92–4.85 (m, 1 H), 3.82 (s, 2 H), 3.33–3.27 (dd, J = 8, 16 Hz, 1 H), 3.05–2.99 (dd, J = 8, 16 Hz, 1 H), 2.84–2.79 (dd, J = 6, 14 Hz, 1 H), 2.72–2.67 (dd, J = 6, 14 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 159.15, 138.17, 129.00, 128.57, 128.06, 127.13, 126.28, 124.99, 120.54, 109.41, 82.19, 36.81, 36.09, 34.97. HRMS (ESI): m/z [M + Na]⁺ Calcd for C₁₆H₁₆NaOS: 279.0814; found: 279.0794.