Efficient Synthesis of Vinyl Sulfones by Manganese-Catalyzed Decarboxylative Coupling of Cinnamic Acids with Aromatic Sulfinic Acid Sodium Salts

Abstract

An efficient synthesis of vinyl sulfones is described. Reactions of cinnamic acids with aromatic sulfinic acid sodium salts in the presence of a catalytic amount of manganese(II) acetate tetrahydrate (5 mol%) in dimethyl sulfoxide (DMSO) afforded the desired vinyl sulfones in good to excellent yields. Notably, the reaction does not need any base or iodide as additive. The use of DMSO as the solvent and running the reaction under air are critical in achieving good yields.

Key words

manganese catalysis - decarboxylation - coupling - cinnamic acids - sodium arenesulfinates - vinyl sulfones

• References

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• 19 General Procedure: To a 25 mL round-bottom flask were added cinnamic acid (0.5 mmol), aromatic sulfinic acid sodium salt (1.5 mmol), Mn(OAc)2·4H₂O (6.13 mg, 0.025 mmol) and DMSO (2 mL). The solution was stirred under air at 110 °C for 12 h. The reaction mixture was cooled to r.t. and washed with sat. aq NaCl (3 ×), extracted with EtOAc, and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel using hexanes–EtOAc (8:1) as the eluent. All compounds are known and were characterized by ¹H NMR, ¹³C NMR, LRMS and their comparison to literature values. (E)-1-Bromo-4-[2-(4-tosyl)vinyl]benzene (3au) ^5c as a representative product: C₁₅H₁₃SO₂Br. Yield: 63%; white solid; mp 163–164 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.75 (d, J = 8.2 Hz, 2 H), 7.51 (d, J = 15.4 Hz, 1 H), 7.45 (d, J = 8.4 Hz, 2 H), 7.27 (t, J = 7.6 Hz, 4 H), 6.77 (d, J = 15.4 Hz, 1 H), 2.37 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.5, 139.4, 136.4, 131.3, 130.3, 128.9, 128.7, 127.3, 126.7, 124.4, 20.6. MS: m/z = 337 (M⁺).