Reactions of Propargylic Bromides with Sodium Sulfinates

Abstract

A one-pot, palladium-catalyzed synthesis of substituted 2,3-bissulfonylpropenes starting with propargylic bromides and sodium sulfinates (RSO₂Na) in the presence of n-Bu₄NF under refluxing aqueous 1,4-dioxane conditions for eight hours in moderate yields is described.

Key words

cross-coupling - domino reaction - elimination - sulfones - palladium

• References and Notes

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For palladium-catalyzed cross-coupling with aryl sulfinates, see:
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• 9 Representative Synthetic Procedure of Skeleton 1 n-Bu₄NF (1.0 M in THF, 0.2 mL, 0.2 mmol) was added to a solution of propargyl bromide (2a) (80% in toluene, 150 mg, 1.0 mmol) or 1-bromopent-2-yne (2b, 150 mg, 1.0 mmol) in 1,4-dioxane (5 mL) at r.t. Then, RSO₂Na 3 (3.0 mmol) in hot H₂O (1 mL) was slowly added to the reaction mixture. The reaction mixture was stirred at r.t. for 10 min. Next, Pd/C (10% in carbon, 11 mg, 0.1 mmol) was added to the stirred solution at r.t. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled, filtered, washed, and concentrated under reduced pressure. The residue was diluted with H₂O (10 mL), and the mixture was extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude product. Purification on silica gel (hexanes–EtOAc, 6:1 to 2:1) afforded skeleton 1. Compound 1e: yield 82% (287 mg); colorless solid; mp 154–155 °C. ESI-HRMS: m/z calcd for C₁₇H₁₉O₄S₂ [M⁺ + 1]: 351.0725; found: 351.0726. ¹H NMR (400 MHz, CDCl₃): δ = 7.62–7.57 (m, 4 H), 7.28–7.25 (m, 4 H), 6.64 (d, J = 0.8 Hz, 1 H), 6.49 (d, J = 0.8, 1.6 Hz, 1 H), 4.02 (d, J = 1.2 Hz, 2 H), 2.43 (s, 3 H), 2.42 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.29, 145.09, 139.67, 134.74, 134.69, 130.43, 129.95 (2×), 129.79 (2×), 128.48 (2×), 128.39 (2×), 54.05, 21.66, 21.64. Single-crystal X-ray diagram: Crystal of 1e was grown by slow diffusion of EtOAc into a solution of 1e in CH₂Cl₂ to yield colorless prisms. The compound crystallizes in the monoclinic crystal system, space group P121/c1, a = 15.6737(5) Å, b = 11.2694(4) Å, c = 19.6400(6) Å, V = 3298.69(19) ų, Z = 8, d _calcd = 1.411 g/cm³, F(000) = 1472, 2θ range 2.11–26.39°; R indices (all data): R1 = 0.1105, wR2 = 0.2077. Compound 1m: yield 82% (379 mg); colorless solid; mp 106–108 °C. ESI-HRMS: m/z calcd for C₂₅H₃₅O₄S₂ [M⁺ + 1]: 463.1977; found: 463.1974. ¹H NMR (400 MHz, CDCl₃): δ = 7.71 (d, J = 8.4 Hz, 2 H), 7.66 (d, J = 8.4 Hz, 2 H), 7.32 (J = 8.0 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.20 (t, J = 7.6 Hz, 1 H), 4.17 (s, 2 H), 2.71–2.65 (m, 4 H), 2.37–2.30 (m, 2 H), 1.65–1.57 (m, 4 H), 1.38–1.30 (m, 4 H), 1.09 (t, J = 7.6 Hz, 3 H), 0.93 (t, J = 7.6 Hz, 3 H), 0.92 (t, J = 7.6 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 152.91, 150.03, 149.35, 136.65, 136.25, 131.20, 129.20 (2×), 129.11 (2×), 128.43 (2×), 128.40 (2×), 53.93, 35.62, 35.59, 33.10 (2×), 23.69, 22.23, 22.19, 13.82 (2×), 12.49.Single-crystal X-ray diagram: Crystal of 1m was grown by slow diffusion of EtOAc into a solution of 1m in CH₂Cl₂ to yield colorless prisms. The compound crystallizes in the monoclinic crystal system, space group P121/c1, a = 29.984 (3) Å, b = 5.2734(5) Å, c = 15.4864(17) Å, V = 2408.6(4) ų, Z = 4, d _calcd = 1.276 g/cm³, F(000) = 992, 2θ range 0.69–26.40°; R indices (all data): R1 = 0.1069, wR2 = 0.1900.
• 10 The RSO₂Na 3 is prepared in accordance with the known method, see: Crowell TA, Halliday BD, McDonald JH. III, Indelicato JM, Pasini CE, Wu EC. Y. J. Med. Chem. 1989; 32: 2436
• 11 CCDC 942165 (1e), 957847 (1m), 942167 (4), 942166 (5a), and 942219 (10b) contain the supplementary crystallographic data for this paper. This data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone]; E-mail: [e-mail]].
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