Facile Synthesis of β-Keto Sulfones Employing Fenton’s Reagent in DMSO

Dedicated to the memory of Professor Alexander V. Butin, colleague and close friend

Abstract

A new facile method for the synthesis of β-keto sulfones employing xanthates, DMSO, and Fenton’s reagent is described. The reaction proceeds under very mild conditions providing a cost-effective straightforward approach to various β-keto sulfones in high yields.

Key words

β-keto sulfones - sulfones - xanthates - dimethyl sulfoxide - Fenton’s reagent - radical reaction

• References and Notes


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• 22 Representative Experimental Procedure for the Synthesis of Compound 3a 34% H₂O₂ (2 mL, 20 mmol) was added to a cooled solution of FeSO₄·7Н₂О (2.78 g, 10 mmol) in DMSO (40 mL), and the mixture was stirred for 30 min at 5–10 °C. Then, xanthate 1a (2.4 g, 10 mmol), FeSO₄·7Н₂О (2.78 g, 10 mmol), and H₂O₂(2 mL, 20 mmol) were added and the reaction mixture was stirred for 30 min at 5–10 °C and, then, 2 h at r.t. (TLC control). The reaction mixture was poured into H₂O (30 mL) and extracted with EtOAc (4 × 50 mL). The combined organic phases were washed with brine, dried over anhydrous Na₂SO₄, filtered, and evaporated under reduced pressure. The resulting crude mixture of products was purified by silica column chromatography using EtOAc–PE (1:4) as eluents. The yield of compound 3a was 1.71 g (86%). Characterization Data of Representative Compounds 3
  2-(Methylsulfonyl)-1-phenylethanone (3a) ²³ Pale yellow solid (1.71 g, isolated yield 86%); mp 107–109 °C (PE–EtOAc = 2:1), lit. 86–90 °C.^{23 1}H NMR (400 MHz, DMSO-d ₆): δ = 8.10–7.97 (m, 2 H), 7.72 (m, 1 H), 7.58 (dd, J = 10.7, 4.9 Hz, 2 H), 5.11 (s, 2 H), 3.16 (s, 3 H) ppm. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 190.59, 136.34, 134.75, 129.50, 129.31, 61.23, 42.51 ppm. ESI-HRMS: m/z calcd for C₉H₁₀O₃SNa [M + Na]⁺: 221.0248; found: 221.0242. Ethyl 2-(Methylsulfonyl)acetate (3l)²⁴ Colorless oil (1.295 g, isolated yield 78%). ¹H NMR (400 MHz, CDCl₃): δ = 4.25 (q, J = 7.1 Hz, 2 H), 3.99 (s, 2 H), 3.12 (s, 3 H), 1.29 (t, J = 7.1 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 163.10, 62.65, 59.12, 41.62, 13.95 ppm. ESI-HRMS: m/z calcd for C₅H₁₀O₃SNa [M + Na]⁺: 189.0197; found: 189.0189.
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