Catalytic application of a Ru-alkylidene in the nucleophilic addition of several carboxylic acids on terminal alkynes and the homocoupling of 1-alkynes

Thermal treatment of Ru-alkylidene (4) bearing a triazol-5-ylidene (NHC) ligand (2) at 110 degreesC and addition of a terminal alkyne generates a ruthenium vinylidene. The thermolysed Ru-alkylidene catalyses the vinylation and dimerisation of 1-alkynes. The nucleophilic addition of acetic acid on terminal alkynes proceeds smoothly and regioselective towards the Markovnikov addition. The addition reaction can be tuned by changing the acidity of the carboxylic acid. At increasing acidity, higher conversion of the triple bond is obtained and the vinylation/dimerisation ratio increases. The direct coupling between two 1-alkynes shows a reactivity order, which decreases from 1-octyne > 1,7-octadiyne > phenylacetylene > 3,3 dimethyl-1-butyne. The regioselectivity is strongly dependent on the nature of the terminal alkyne. (C) 2003 Elsevier Science B.V. All rights reserved.