Iron-Catalyzed Oxidative Sulfonylation of Enol Acetates: An Environmentally Benign Approach to β-Keto Sulfones

Vinod K. Yadav; Vishnu P. Srivastava; Lal Dhar S. Yadav

doi:10.1055/s-0035-1560830

Synlett, Table of Contents

Synlett 2016; 27(03): 427-431
DOI: 10.1055/s-0035-1560830

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Iron-Catalyzed Oxidative Sulfonylation of Enol Acetates: An Environmentally Benign Approach to β-Keto Sulfones

Vinod K. Yadav

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com

,

Vishnu P. Srivastava

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com

,

Lal Dhar S. Yadav*

Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad 211002, India Email: ldsyadav@hotmail.com

› Author Affiliations

Abstract

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Abstract

The first application of iron-catalyzed sulfonylation of aryl enol acetates with sulfonyl hydrazides for the construction of β-keto sulfones under aerobic conditions is reported. The present protocol, which utilizes an inexpensive iron salt as the catalyst, readily available sulfonyl hydrazides as the sulfonylating reagents, and air as oxidant under mild conditions, provides a cost-effective and environmentally benign approach to various β-keto sulfones.

Key words

oxidation - ketones - catalysis - addition - sulfonylation - β-keto sulfones

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References

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22 General Procedure for the Synthesis of β-Keto Sulfones 3 Enol acetate 1 (1 mmol), sulfonyl hydrazide 2 (1.5 mmol), FeCl₃ (10 mol%), and THF (3 mL) were added to a flask open to the air, and the mixture was stirred at 70 °C for 5–6 h (Scheme 2). After completion of the reaction (monitoring by TLC), H₂O (5 mL) was added, and the mixture was extracted with EtOAc (3 × 5 mL). The combined organic phases were dried over anhydrous Na₂SO₄, filtered, and evaporated under reduced pressure. The resulting crude product was purified by silica gel chromatography using a mixture of hexane–EtOAc (4:1) as eluent to afford an analytically pure sample of product 3. All the compounds 3 are known and were characterized by comparison of their spectroscopic data with those reported in the literature.^4d,5b,19d,21 Characterization Data of Representative Compounds 3 Compound 3a:^4d,5b solid; 91% yield. ¹H NMR (400 MHz, CDCl₃): δ = 7.95 (d, J = 7.6 Hz, 2 H), 7.80 (t, J = 8.5 Hz, 2 H), 7.61 (t, J = 7.5 Hz, 1 H), 7.44 (t, J = 7.8 Hz, 2 H), 7.35 (d, J = 7.8 Hz, 2 H), 4.71 (s, 2 H), 2.47 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 188.27, 145.53, 135.85, 135.84, 134.43, 129.98, 129.46, 128.96, 128.73, 63.86, 21.87. MS (EI): m/z = 274 [M⁺]. Anal. Calcd for C₁₅H₁₄O₃S: C, 65.67; H, 5.14; S, 11.69. Found: C, 65.89; H, 4.93; S, 11.53. Compound 3i:^19d,21b solid; 92% yield. ¹H NMR (400 MHz, CDCl₃): δ = 7.86 (d, J = 8.4 Hz, 2 H), 7.81 (d, J = 8.4 Hz, 2 H), 7.30–7.26 (m, 2 H), 7.24–7.20 (m, 2 H), 4.70 (s, 2 H), 2.44 (s, 3 H), 2.44 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 187.65, 145.38, 145.15, 136.11, 133.46, 129.70, 129.39, 129.37, 128.50, 63.56, 21.59, 21.52. MS (EI): m/z = 288 [M⁺]. Anal. Calcd for C₁₆H₁₆O₃S: C, 66.64; H, 5.59; S, 11.12. Found: C, 66.80; H, 5.43; S, 11.39. Compound 3j: ^4d,21a solid; 86% yield. ¹H NMR (400 MHz, CDCl₃): δ = 7.91–7.87 (m, 4 H), 7.73 (t, J = 7.5 Hz, 1 H), 7.54 (t, J = 7.6 Hz, 2 H), 7.46 (d, J = 8.5 Hz, 2 H), 4.73 (s, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 186.97, 141.30, 138.67, 134.51, 134.15, 130.89, 129.41, 129.38, 128.66, 63.69. MS (EI): m/z = 294, 296 [M⁺, M⁺ + 2]. Anal. Calcd for C₁₄H₁₁ClO₃S: C, 57.05; H, 3.76; S, 10.88. Found: C, 57.33; H, 3.89; S, 10.98.