Highly Efficient Copper- and Palladium-Free One-Pot Coupling of Alkynes with Sodium Carboxylate Salts Using Cyanuric and Magnesium Chlorides

Abstract

A facile and highly efficient copper- and palladium-free procedure for the one-pot synthesis of ynones via coupling of sodium carboxylate salts with alkynes is described. In this method, cross-coupling of terminal alkynes with a mixture of structurally diverse sodium carboxylate salts, cyanuric chloride and triethylamine in the presence of magnesium chloride furnishes the corresponding ynones in good to excellent yields at room temperature.

one-pot synthesis - alkyne - cyanuric chloride - sodium carboxylate salt - ynone

References and Notes

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Similar reaction conditions were employed for carboxylic acid, except that Et₃N (6.6 equiv) was employed

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General procedure for coupling of alkynes with sodium carboxylate salts using cyanuric chloride: To a solution of sodium carboxylate salt (3.3 mmol) in anhydrous MeCN (5 mL), was added TCT (1 mmol) and the reaction mixture was stirred at r.t. for 10 min. A solution of the appropriate alkyne (3 mmol), Et₃N (3.3 mmol) and MgCl₂ (3.3 mmol) in anhydrous MeCN (5 mL) was added and the solution was stirred for a further 50-110 min (until TLC indicated completion of the reaction, see Table  [5] ). The solution was filtered and the solvent was evaporated under vacuum. The remaining foam was then diluted in CHCl₃ (50 mL) and subsequently washed with H₂O (2 × 50 mL). The organic layer was dried (Na₂SO₄) and evaporated. The crude product was purified by short column chromatography on silica gel (n-hexane-EtOAc, 20:1).