KI/K₂S₂O₈-Mediated α-C–H Sulfenylation of Carbonyl Compounds with (Hetero)Aryl Thiols

Abstract

A new and facile KI/K₂S₂O₈-mediated α-C–H sulfenylation of carbonyl compounds with (hetero)aryl thiols was developed for the formation of C–S bond at room temperature. This method provided a simple process for the synthesis of β-keto thioethers in moderate to excellent yields. A variety of carbonyl compounds and (hetero)aryl thiols were tolerated in this reaction.

Key words

sulfenylation - carbonyl compounds - (hetero)aryl thiols - room temperature - β-keto thioethers

• References and Notes

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• 12 Procedure for the Synthesis of 2-{Benzo[d]thiazol-2-ylthio}-1-phenylethanone The mixture of acetophenone (1.0 mmol), benzo[d]thiazole-2(3H)-thione (0.5 mmol, 1 equiv), KI (20 mol%), K₂S₂O₈ (0.6 equiv), and DMSO (1 mL) was stirred at r.t. for 24 h. Afterwards, the reaction mixture was washed with aq NaCl (10 ml) and extracted with EtOAc (15 mL, 3×). The obtained top organic layer was dried with anhydrous MgSO₄. The mixture was concentrated in vacuo, and the residue was purified by column chromatography on silica gel (EtOAc/n-hexane = 5%) to afford the pure product. White solid (92%). ¹H NMR (400 MHz, CDCl₃): δ = 8.07–8.05 (m, 2 H), 7.82–7.80 (m, 1 H), 7.54–7.22 (m, 1 H), 7.61 (t, J = 7.6 Hz, 2 H), 7.52–7.39 (m, 2 H), 7.31–7.28 (m, 2 H), 4.97 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 192.93, 165.24, 152.81, 135.45, 135.42, 133.81, 128.76, 128.54, 126.02, 124.38, 121.45, 121.04, 40.99.