Addition of carboxylic acids to alkynes catalysed by ruthenium complexes

Ligand‐Controlled Regio‐ and Stereoselective Addition of Carboxylic Acids Onto Terminal Alkynes Catalyzed by Carbonylruthenium(0) Complexes

“…The organic products were characterized using 1 H NMR techniques, and their splitting patterns and chemical shifts were matched to those reported in literatures. [11] When phenylacetylene was used as a reagent in the hydrocarboxylation reaction (Table 1), it was observed that the substituent group (Ph, Me or tBu) on the carboxylic acid reagent did not affect the enol ester yield significantly. However, it was found that when trinuclear complexes 1 and 2 were used the system gave a smaller enol ester yield (Ͻ 90 %) compared to the mononuclear systems under the same reaction conditions.…”

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

“…In this context, in their pioneering works, Rotem and Shvo studied the addition of different carboxylic acids to diphenylacetylene, 4-octyne and DMAD (dimethyl acetylenedicarboxylate) using [Ru3(CO)12] (2 mol%) as catalyst (Scheme 2). 57,67 As expected, the reactions, which were performed in toluene at 145 °C, proceeded at comparatively much lower rates than those encountered when employing terminal alkynes as substrates. Concerning the reactions outcome, starting from 4-octyne and DMAD the enol esters 1 were obtained stereoselectively as a result of the syn-addition of the carboxylic acid to the C≡C bond.…”

Synthesis and structure of [Ru(dppe)2(CH3CN)Cl][BPh4] and its catalytic application to anti-Markovnikov addition of carboxylic acids to terminal alkynes

“…Rotem and Shvo reported the first ruthenium catalyzed addition of carboxylic acid to alkyne using Ru 3 (CO) 12 as catalyst [25,26], which was followed by a large number of reports on ruthenium catalyzed addition of carboxylic acid to alkynes [27e36]. Addition of carboxylic acid to alkynes affords three possible isomers (Scheme 1) and most of the reported reactions afford more than one isomers.…”