A Combination System of p-Toluenesulfonic Acid and Acetic Acid for the Hydration of Alkynes

Abstract

A simple combination system of p-toluenesulfonic acid/acetic acid has been developed for efficient hydration of alkynes. The corresponding ketones can be obtained in good to excellent yields under mild conditions. The mechanism of the reaction was disclosed unambiguously which was a stepwise process (addition and then hydrolysis). Furthermore, this system was proved to be powerful that has the potential to be used to synthesize vinyl 4-methylbenzenesulfonates.

Key words

hydration - alkynes - ketones - hydrolysis - vinyl sulfonates

• References and Notes

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• 15 General Procedures for Alkyne Hydration The corresponding alkyne (1 mmol) was added to a solution of PTSA·H₂O (1 mmol, 0.190 g), AcOH (0.5 mL) in CH₂Cl₂ (1.0 mL). The reaction was then sealed and stirred at the indicated temperature (°C) and for the indicated amount of times (h) in Table 2. After completion, sat. aq NaHCO₃ (10 mL) was added to quench the reaction and then extracted with CH₂Cl₂ (3 × 10 mL). The organic layer was dried over Na₂SO₄ and concentrated in vacuo. The residue was purified by column chromatography to give the pure product. Acetophenone (2a) Colorless liquid; yield: 114 mg (95%). ¹H NMR (500 MHz, CDCl₃): δ = 7.95 (d, J = 7.5 Hz, 2 H), 7.56–7.54 (m, 1 H), 7.46–7.43 (m, 2 H), 2.59 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 198.18, 137.16, 133.12, 128.59, 128.33, 26.62.