NaI-Mediated Acetamidosulfenylation of Alkenes with Bunte Salts as Thiolating Reagent Leading to β-Acetamido Sulfides

Abstract

A direct and efficient method for the acetamidosulfenylation reaction of alkenes was developed, in which NaI was used as a catalyst, DMSO as the oxidant, nitriles as both the solvent and nucleophiles and stable, readily available Bunte salts as thiolating reagents. The reactions were carried out under mild conditions generating β-acetamido sulfides in good yields. Moreover, the reaction can be performed when alcohols are used as nucleophiles providing the corresponding β-alkoxysulfides in moderate yields, respectively.

Key words

alkenes - Bunte salts - β-acetamido sulfides - nitriles - nucleophiles

• References and Notes

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• 16 General Procedure for the Synthesis of Compound 4 or 5 NaI (0.06 mmol), H₂O (0.60 mmol) and Bunte salt 2 (0.45 mmol) were added to a solution of nitrile 3 containing alkene 1 (0.30 mmol), followed by the addition of DMSO (0.60 mmol). The reaction mixture was stirred in a sealed tube at 100 °C for 9 h. After completion of the reaction, the reaction mixture was diluted with EtOAc, and quenched with sat. Na₂S₂O₃ solution and extracted with EtOAc (3 × 10 mL). The organic layer was washed with water and dried over anhydrous Na₂SO₄. The solvent was evaporated in vacuo, and the residue was subjected to column chromatography using EtOAc in PE as the eluent to afford the pure target product 4 or 5. Compound 4b was obtained in 82% yield (73.7 mg) according to the general procedure for the synthesis of 4 as a white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.32–7.23 (m, 5 H), 7.12 (s, 4 H), 6.03 (d, J = 8.0 Hz, 1 H), 5.12 (q, J = 8.0 Hz, 1 H), 3.59 (q, J = 12 Hz, 2 H), 2.86–2.74 (m, 2 H), 2.32 (s, 3 H), 1.95 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.5, 138.0, 137.7, 137.4, 129.4, 129.0, 128.5, 127.1, 125.4, 51.8, 37.1, 36.4, 23.4, 21.1. ESI-HRMS: m/z calcd for C₁₈H₂₁NOS [M + Cl]⁺: 334.1027; found: 334.1036. General Procedure for the Synthesis of Compound 7 NaI (0.06 mmol) and 2a (0.45 mmol) was added to a solution of acetonitrile 3a containing styrene 1a (0.30 mmol) and alcohol (100 μL) or 2-allylphenol 6d (0.3 mmol), followed by DMSO (0.60 mmol). The reaction mixture was stirred at 90 °C for 6–9 h. After completion of the reaction, the reaction mixture was diluted with EtOAc, quenched with sat. Na₂S₂O₃ solution and extracted twice with EtOAc (2 × 15 mL). The organic layer was washed with water and dried over anhydrous Na₂SO₄. The solvent was evaporated in vacuo, and the residue was subjected to column chromatography using EtOAc in PE as the eluent to afford the pure target product 7.Compound 7a was obtained in 42% yield (32.7 mg) according to the general procedure for the synthesis of 7 as a colorless liquid. ¹H NMR (400 MHz, CDCl₃): δ = 7.37–7.21 (m, 10 H), 4.31 (q, J = 8.0 Hz, 1 H), 3.69 (q, J = 12.0 Hz, 1 H), 3.42–3.33 (m, 1 H), 2.84 (q, J = 8.0 Hz, 1 H), 2.60 (q, J = 8.0 Hz, 1 H), 1.20 (t, J =8.0 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 141.6, 138.6, 129.0, 129.4, 128.4, 128.4, 127.8, 126.9, 126.7, 82.3, 64.5, 38.7, 37.2, 15.3. ESI-HRMS: m/z calcd for C₁₇H₂₀OS [M + Na]⁺: 295.1127; found: 295.1120.