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DOI: 10.1055/s-0030-1260544
Stereoselective Synthesis of (E)-Alkenyl Sulfones from Alkenes or Alkynes via Copper-Catalyzed Oxidation of Sodium Sulfinates
Publication History
Publication Date:
20 April 2011 (online)
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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.
Key words
alkenyl sulfone - copper catalyst - sodium sulfinate - alkene - alkyne
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- Supporting Information
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References and Notes
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.
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.
In the presence of the proton, the disproportionation of copper ion easily proceeds, see ref. 12.