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DOI: 10.1055/s-2004-831310
Highly Efficient p-Toluenesulfonic Acid-Catalyzed Alcohol Addition or Hydration of Unsymmetrical Arylalkynes
Publikationsverlauf
Publikationsdatum:
26. August 2004 (online)
Abstract
Under a catalytic amount of PTSA in aqueous or alcoholic media, activated unsymmetrical arylalkynes 1 undergo regioselective water or alcohol addition to afford successfully carbonyl compounds 2 in good to excellent yields. This new environmentally metal-free procedure, which afforded only Markovnikov adducts, is characterized by the mildness of acidic conditions and the excellent regio- and chemoselectivity.
Key words
unsymmetrical arylalkyne - hydration - PTSA - ketone - alcohol addition - water
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References
Typical Procedure for the PTSA-Catalyzed Hydration of Unsymmetrical Arylalkynes: To a stirred solution of 1a (162 mg, 1 mmol) in 2 mL of absolute EtOH, was added pTSA monohydrate (38 mg, 0.2 mmol). The mixture was heated at reflux for 5 h, diluted with H2O and extracted with EtOAc. The combined organic layer was washed with brine and dried over anhydrous Na2SO4. After removal of the solvent under vacuo, the crude product was purified by column chromatography on silica gel (CH2Cl2) to afford 196 mg (94%) of 2b as a yellow oil. 3-Ethoxy-1-(4-methoxy-phenyl)propan-1-one (2b): 1H NMR (270 MHz, CDCl3): δ = 7.89 (2 H, d, J = 8.9 Hz), 6.87 (2 H, d, J = 8.9 Hz), 3.79 (2 H, t, J = 6.8 Hz), 3.78 (3 H, s), 3.47 (2 H, q, J = 7.0 Hz), 3.14 (2 H, t, J = 6.7 Hz), 1.14 (3 H, t, J = 7.0 Hz). 13C NMR (67.5 MHz, CDCl3): δ = 196.7, 163.3, 130.2, 130.0, 113.5, 66.3, 65.8, 55.2, 38.4, 14.9. 1-(4-Aminophenyl)-6-hydroxyhexan-1-one (2f): 1H NMR (270 MHz, CD3OD): δ = 7.75 (2 H, d, J = 8.8 Hz), 6.63 (2 H, d, J = 8.8 Hz), 3.55 (2 H, t, J = 6.4 Hz), 2.87 (2 H, t, J = 7.6 Hz), 1.80-1.20 (6 H, m). 13C NMR (67.5 MHz, CD3OD): δ = 201.5, 153.6, 132.1, 126.8, 114.3, 62.3, 38.6, 33.5, 26.7, 26.1. 1-(2-Methoxyphenyl)hexan-1-one (2k): 1H NMR (270 MHz, CDCl3): δ = 7.61 (1 H, dd, J = 7.6 Hz, J = 1.8 Hz), 7.45-7.30 (1 H, m), 7.00-6.85 (2 H, m), 3.84 (3 H, s), 2.92 (2 H, t, J = 7.5 Hz), 1.75-1.55 (2 H, m), 1.35-1.25 (4 H, m), 0.87 (3 H, t, J = 6.9 Hz). 13C NMR (67.5 MHz, CDCl3): δ = 202.9, 158.1, 132.8, 129.9, 128.7, 120.4, 111.4, 55.2, 43.5, 31.4, 23.9, 22.3, 13.7.