Stereoselective Synthesis of (E)-Alkenyl Sulfones from Alkenes or Alkynes via Copper-Catalyzed Oxidation of Sodium Sulfinates

Abstract

Alkenyl sulfones can be stereoselectively synthesized from alkenes or alkynes using sodium sulfinates. The reaction can be performed by a copper-catalyzed oxidation of sodium sulfinates in air. The reaction of alkenes gives (E)-alkenyl sulfones via anti addition of sulfonyl cation and elimination process. Furthermore, the employment of alkynes produces (E)-β-haloalkenyl sulfones in the presence of potassium halides.

alkenyl sulfone - copper catalyst - sodium sulfinate - ­alkene - alkyne

References and Notes

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<A NAME="RU00911ST-11">11</A>

Typical Procedure of Alkenyl Sulfones Using Alkenes
To a mixture of CuI (4.6 mg, 0.024 mmol), bpy (3.7 mg, 0.024 mmol), PhSO₂Na (2a, 59.4 mg, 0.33 mmol), and KI (24.9 mg, 0.15 mmol) in DMSO (0.15 mL) and AcOH (0.15 mL) was added styrene 1a (31.2 mg, 0.3 mmol), and the mixture was stirred at 100 ˚C for 18 h in air. After the residue was dissolved in Et₂O, the solution was washed with sat. NaHCO₃, H₂O, and sat. NaCl and dried over anhyd MgSO₄. Chromatography on silica gel (30% Et₂O-hexane) gave phenyl (E)-2-phenylethenyl sulfone (3aa, 68.7 mg, 94%). ^¹H NMR (270 MHz, CDCl₃): δ = 7.96-7.93 (m, 2 H), 7.68 (d, J = 15.5 Hz, 1 H), 7.58-7.30 (m, 8 H), 6.87 (d, J = 15.5 Hz, 1 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 142.4, 140.6, 133.3, 132.2, 131.1, 129.3, 128.9, 128.5, 127.6, 127.2. IR (CHCl₃): 3061, 3025, 1613, 1447, 1306 cm^-¹. Anal. Calcd for C₁₄H₁₂O₂S: C, 68.83; H, 4.95. Found: C, 68.75; H, 5.13.

<A NAME="RU00911ST-12">12</A> The stereochemistry of these compounds was determined by the comparison with references or authentic samples. Compounds 7cb, 7db, (Z)-3hb, and (Z)-3ib were prepared by oxidation of the corresponding alkenyl sulfides using MCPBA. For the preparation of alkenyl sulfides, see: Taniguchi N. Tetrahedron  2009,  65:  2782 ; see ref. 15a

<A NAME="RU00911ST-13">13</A>

Typical Procedure of β-Haloalkenyl Sulfones Using Alkynes
To a mixture of CuI (4.6 mg, 0.024 mmol), bpy (3.7 mg, 0.024 mmol), PhSO₂Na (2a, 59.4 mg, 0.33 mmol), and KBr (39.3 mg, 0.33 mmol) in AcOH (0.3 mL) was added phenylacetylene 1a (30.6 mg, 0.3 mmol), and the mixture was stirred at 100 ˚C for 18 h in air. After the residue was dissolved in Et₂O, the solution was washed with sat. NaHCO₃, H₂O, and sat. NaCl and dried over anhyd MgSO₄. Chromatography on silica gel (40% Et₂O-hexane) gave (E)-1-phenylsulfonyl-2-bromo-2-phenylethene (7aa, 60.7 mg, 63%). ^¹H NMR (270 MHz, CDCl₃): δ = 7.61-7.51 (m, 3 H), 7.42-7.30 (m, 7 H), 7.17 (s, 1 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 140.2, 138.7, 135.9, 134.1, 133.5, 130.4, 128.9, 128.5, 127.9, 127.7. IR (CHCl₃): 3056, 1611, 1590, 1446, 1324 cm^-¹. Anal. Calcd for C₁₄H₁₁O₂SBr: C, 52.03; H, 3.43. Found: C, 51.42; H, 3.17.

<A NAME="RU00911ST-14">14</A>

In the presence of the proton, the disproportionation of copper ion easily proceeds, see ref. 12.

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