Eosin Y-Sensitized Photocatalytic Reaction of Tertiary Aliphatic Amines with Arenesulfonyl Chlorides under Visible-Light Irradiation

Abstract

A mild, practical, and environmentally friendly route to vinyl sulfones and sulfonamides has been developed based on the reaction of aliphatic amines with arenesulfonyl chlorides in the presence of eosin Y as a photocatalyst under visible light. The method permits the selective formation of vinyl sulfones or sulfonamides, depending on the oxidation environment and solvent. A wide range of products were obtained in moderate to good yields under the optimized conditions.

Key words

vinyl sulfones - sulfonamides - eosin Y - photoredox catalysis - amines - arenesulfonyl chlorides

• References and Notes

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• 61 (E)-N,N-Diethyl-2-(4-toluenesulfonyl)ethylenamine (3a); Typical Procedure A 10 mL round-bottomed flask equipped with magnetic stirring bar was charged with TsCl (1a; 0.2 mmol), Et₃N (2a; 1 mmol), eosin Y (3 mol%), K₂HPO₄ (1.5 equiv), and 1:2 EtOH–acetone (6 mL). The solution was then irradiated with 3 W blue LEDs at –5 to 5 °C under air. When the reaction was complete (TLC), the solvent was removed under reduced pressure and the crude product was purified by column chromatography [silica gel, PE–EtOAc (5:1)] to give a brown oil; yield: 31.48 mg (67%). ¹H NMR (400 MHz, CDCl₃): δ = 7.75 (d, J = 8.2 Hz, 2 H), 7.31 (d, J = 12.7 Hz, 1 H), 7.27 (d, J = 8.0 Hz, 2 H), 4.91 (d, J = 12.7 Hz, 1 H), 3.18 (br d, 4 H), 2.41 (s, 3 H), 1.17 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 148.5, 142.3, 141.8, 128.5, 125.9, 91.4, 49.8, 42.4, 21.2, 14.5 11.0. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₃H₁₉NNaO₂S⁺: 276.1020; found: 276.1029.
• 62 N,N-Diethyl-4-toluenesulfonamide (4a); Typical Procedure A 10 mL round-bottomed flask equipped with magnetic stirring bar was charged with TsCl (1a; 0.2 mmol), Et₃N (2a; 1 mmol), eosin Y (3 mol%), K₂HPO₄ (1.5 equiv), and 1:1 MeCN–H₂O (6 mL). The solution was then irradiated with 12 W blue LEDs at r.t. under an O₂ atmosphere. When the reaction was complete (TLC), the solvent was removed under reduced pressure and the crude product was purified by column chromatography [silica gel, PE–EtOAc (5:1)] to give a white solid; yield: 34.06 mg (75%); mp 60–62 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.70 (d, J = 8.1 Hz, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 3.23 (q, J = 7.2 Hz, 4 H), 2.43 (s, 3 H), 1.13 (t, J = 7.1 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 142.8, 137.2, 129.4, 126.9, 41.9, 21.3, 14.0. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₁H₁₇NNaO₂S⁺: 250.0872; found: 250.0898.