95865-57-9

Upstream product

• 627-19-0 1-Pentyne 
• 65-85-0 benzoic acid 

Downstream Products

• 39180-02-4 benzoate de pentyle-2 
• 39180-02-4 (R)-benzoic acid 1-methylbutyl ester 
• 39180-02-4 (S)-benzoic acid 1-methylbutyl ester 

Relevant academic research and scientific papers

Selective Addition of Unsaturated Carboxylic Acids to Terminal Acetylenes Catalyzed by Bis(η5-cyclooctadienyl)ruthenium(II)-Tri-n-butylphosphine. A Novel Synthesis of Enol Esters

Unsaturated carboxylic acids such as methacrylic acid, crotonic acid, vinylacetic acid, and sorbic acid and aromatic carboxylic acids reacted with terminal acetylenes in the presence of a catalytic amount of bis(η5-cyclooctadienyl)ruthenium-P-n

Regioselective Formation of Enol Esters from the Ruthenium-Catalyzed Markovnikov Addition of Carboxylic Acids to Alkynes

The ruthenium complexes [Ru(CO)2(P(p-C6H4-X)3)2(O2CPh)2] (1a, X = CF3; 1b, X = Cl; 1c, X = H; 1d, X = Me; 1e, X = OMe) were successfully applied in the regioselective Markovnikov addition of carboxylic acids to terminal alkynes, yielding valuable enol esters. Catalyst screening revealed a significant influence of phosphine's electronic nature on activity and selectivity. The highest activity was achieved with catalyst 1a, featuring the most electron-withdrawing phosphine ligand. Selectivity and activity could be further improved by the addition of catalytic amounts of AgOTf. Moreover, excellent selectivities with up to 99% of the Markovnikov product were achieved. The electronic influence of the substrates on the reaction rate was quantified by Hammett plots. By the use of electron-rich alkynes or highly acidic carboxylic acids, the reaction rate could be increased. Hence, the addition of highly acidic pentafluorobenzoic acid to electron-rich 4-methoxyphenylacetylene can even be carried out quantitatively at 25°C within 4 h. Furthermore, a broad range of simple as well as electronically or sterically challenging substrates could be isolated in good to excellent yields with high regioselectivity and under mild reaction conditions (25-70°C). The best reported activities and selectivities were obtained for the conversion of aromatic alkynes.

Asymmetric hydrogenation of 1-alkyl and 1-aryl vinyl benzoates: A broad scope procedure for the highly enantioselective synthesis of 1-substituted ethyl benzoates

The enantioselective hydrogenation of enol esters of formula CH2=C(OBz)R with rhodium catalysts based on phosphine-phosphite ligands (P-OP) has been studied. The reaction has a broad scope, and it is suitable for the preparation of products pos

Highly enantioselective Rh-catalysed hydrogenation of 1-alkyl vinyl esters using phosphine-phosphoramidite ligands

MatPhos, a good mate for hard tasks: The asymmetric hydrogenation of 1-alkyl vinyl esters, thwarted so far by mediocre ee values and low activities, can now be achieved with MatPhos/Rh catalysts with ee values of 96-99 % for a variety of substrates at low catalyst loadings (0.1-1 mol %) and under mild conditions (5-20 bar H2, room temperature). After hydrolysis, the corresponding chiral secondary alkyl alcohols can be obtained in high enantiopurities providing a general and practical route to this important product class. Copyright

Highly enantioselective hydrogenation of 1-alkylvinyl benzoates: A simple, nonenzymatic access to chiral 2-alkanols

Going chiral! Highly enantioselective catalytic hydrogenations of enol esters 1 by using a Rh catalyst bearing a P?￡?OP ligand are described (see scheme; NBD=norbornadiene). The catalytic system has a broad scope and allows the preparation of a wide range of chiral esters 2 bearing diverse alkyls or a benzyl group with high enantioselectivities. These esters can easily be converted in highly enantioenriched 2-alkanols. Copyright

Ruthenium(IV)-catalyzed markovnikov addition of carboxylic acids to terminal alkynes in aqueous medium

The dimeric bis(allyl)ruthenium(IV) complex [{RuCl(μ-Cl)( η3:η3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) (5) and several mononuclear species trans-[RuCl2(η3: η3-C10H16)(L)] (L = two-electron-donor ligand) (6) derived from 5 have been checked as catalysts for the addition of carboxylic acids onto terminal alkynes using water as a green reaction medium. The best results in terms of activity and regioselectivity were obtained with the mononuclear derivative trans-[RuCl2(η3: η3-C10H16)(PPh3)] (6a), which was able to promote the selective Markovnikov addition of both aromatic and aliphatic carboxylic acids to a large variety of terminal alkynes, enynes, and diynes as well as propargylic alcohols. In this way, a wide number of enol esters and β-oxo esters could be synthesized in moderate to good yields under mild conditions (60 °C) in an aqueous medium.

Ruthenium-Catalyzed Selective Addition of Carboxylic Acids to Alkynes.A Novel Synthesis of Enol Esters

Carboxylic acids react with alkynes in the presence of a catalytic amount of bis(ν5-cyclooctadienyl)ruthenium/trialkylphosphine/maleic anhydride in toluene at 60-80 deg.C to give enol esters having a terminal methylene group in good to excellent yields with high regioselectivity.The deuterium distributions in the products of the reaction of acetic acid-d with 1-hexyne and ethyl propargyl carbonate were examined.Kinetic measurments revealed that the rate has first-order dependence on carboxylic acid, alkyne, and the initial concentration of the ruthenium catalyst.