819-97-6Relevant articles and documents
Enantioselective transesterification catalysis by nanosized serine protease subtilisin Carlsberg particles in tetrahydrofuran
Castillo, Betzaida,Delgado, Yamixa,Barletta, Gabriel,Griebenow, Kai
experimental part, p. 2175 - 2180 (2010/04/29)
Enzyme catalysis in organic solvents is a powerful tool for stereo-selective synthesis but the enantioselectivity is still hard to predict. To overcome this obstacle, we employed a nanoparticulate formulation of subtilisin Carlsberg (SC) and designed a series of 14 structurally related racemic alcohols. They were employed in the model transesterification reaction with vinyl butyrate and the enantioselectivities were determined. In general, short alcohol side chains led to low enantioselectivties, while larger and bulky side chains caused better discrimination of the enantiomers by the enzyme. With several bulky substrates high enantioselectivities with E>100 were obtained. Computational modeling highlighted that key to high enantioselectivity is the discrimination of the R and S substrates by the sole hydrophobic binding pocket based on their size and bulkiness. While bulky S enantiomer side chains could be accommodated within the binding pocket, bulky R enantiomer side chains could not. However, when also the S enantiomer side chain becomes too large and does not fit into the binding pocket anymore, enantioselectivity accordingly drops.
Carboxylic acids supported on silica: A smooth acylating agent for alcohols
Da Graca Nascimento, Maria,Zanotto, Sandra Patricia,Scremin, Marivania,Rezende, Marcos Caroli
, p. 2715 - 2721 (2007/10/03)
An alternative procedure for the esterification of alcohols by short-chain carboxylic acids supported on silica is presented.
CATALYSED LIQUID PHASE OXIDATION OF ACETALS BY MOLECULAR OXYGEN
Vcelak, Jaroslav,Klimova, Miroslava,Chvalovsky, Vaclav
, p. 847 - 866 (2007/10/02)
Nine different acetals have been oxidized in the presence of Co(OOCCH3)2*4H2O under isobaric conditions (0.1 - 0.2 MPa O2) while following the uptake of molecular oxygen.The reactivity of acetals was expressed by the rate constants of the autocatalytic model of oxidation.The main product of the oxidation are alcohols, esters and acids.The distribution of products and the total reactivity of acetals are controlled by the structure of both parts of acetal molecule.The dominant effects of the course of the reaction exerts the type of carbon atoms on which radicals are formed.The oxidation is accompanied by consecutive and co-oxidation reactions, by deactivation of the catalysts and by decarbonylation of intermediate products.The effect of oxygen pressure is reported and the more detailed radical mechanism of the oxidation is proposed.