CEQUINOR   05415
CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Unidad Ejecutora - UE
artículos
Título:
Theoretical Modeling of the Interaction Chiral Modifier/Substrate as a Key Step in the Enantioselective Hydrogenation of a-ketoesters and Vicinal Diketones
Autor/es:
JOSE FERNANDO RUGGERA; AYELÉN GAZQUEZ; REINALDO PIS DIEZ; MÓNICA LAURA CASELLA
Revista:
Current Catalysis
Editorial:
Bentham Science Publishers
Referencias:
Año: 2014 vol. 3 p. 213 - 213
ISSN:
2211-5447
Resumen:
This paper deals with the computational modeling of the chiral modifier/substrate interaction for chiral modifi-ers studied in our laboratory, different from those conventionally used in enantioselective hydrogenation reactions. (S)-(+)-1-aminoindane and (R)-(-)-1-aminoindane were chosen as chiral modifiers and the selected substrates were methyl py-ruvate, ethyl pyruvate and 1-ethyl-4,4-dimethyl-pyrrolidinae-2,3,5-trione.The geometry of each of the chiral modifier/substrate complexes was optimized using DFT calculations and a BLYP func-tional. The theoretical enantiomeric excess was calculated from the energy of each of the proposed complexes. The calcu-lations were carried out considering different reaction solvents through the use of COSMO program.It was found that this simple model allows predicting the experimental values of both the sense of enantiodifferentiationand the enantiomeric excess with a good approximation. It was also able to predict the inversion of configuration whenusing the (S)-(+)-1-aminoindane as chiral modifier in polar solvents such as acetic acid and 2-propanol. This paper deals with the computational modeling of the chiral modifier/substrate interaction for chiral modifiers studied in our laboratory, different from those conventionally used in enantioselective hydrogenation reactions. (S)- (+)-1-aminoindane and (R)-(-)-1-aminoindane were chosen as chiral modifiers and the selected substrates were methyl pyruvate, ethyl pyruvate and 1-ethyl-4,4-dimethyl-pyrrolidinae-2,3,5-trione. The geometry of each of the chiral modifier/substrate complexes was optimized using DFT calculations and a BLYP functional. The theoretical enantiomeric excess was calculated from the energy of each of the proposed complexes. The calculations were carried out considering different reaction solvents through the use of COSMO program. It was found that this simple model allows predicting the experimental values of both the sense of enantiodifferentiation and the enantiomeric excess with a good approximation. It was also able to predict the inversion of configuration when using the (S)-(+)-1-aminoindane as chiral modifier in polar solvents such as acetic acid and 2-propanol. - See more at: http://eurekaselect.com/119154#sthash.W69M4rz9.dpuf This paper deals with the computational modeling of the chiral modifier/substrate interaction for chiral modifiers studied in our laboratory, different from those conventionally used in enantioselective hydrogenation reactions. (S)- (+)-1-aminoindane and (R)-(-)-1-aminoindane were chosen as chiral modifiers and the selected substrates were methyl pyruvate, ethyl pyruvate and 1-ethyl-4,4-dimethyl-pyrrolidinae-2,3,5-trione. The geometry of each of the chiral modifier/substrate complexes was optimized using DFT calculations and a BLYP functional. The theoretical enantiomeric excess was calculated from the energy of each of the proposed complexes. The calculations were carried out considering different reaction solvents through the use of COSMO program. It was found that this simple model allows predicting the experimental values of both the sense of enantiodifferentiation and the enantiomeric excess with a good approximation. It was also able to predict the inversion of configuration when using the (S)-(+)-1-aminoindane as chiral modifier in polar solvents such as acetic acid and 2-propanol. - See more at: http://eurekaselect.com/119154#sthash.W69M4rz9.dpuf This paper deals with the computational modeling of the chiral modifier/substrate interaction for chiral modifiers studied in our laboratory, different from those conventionally used in enantioselective hydrogenation reactions. (S)- (+)-1-aminoindane and (R)-(-)-1-aminoindane were chosen as chiral modifiers and the selected substrates were methyl pyruvate, ethyl pyruvate and 1-ethyl-4,4-dimethyl-pyrrolidinae-2,3,5-trione. The geometry of each of the chiral modifier/substrate complexes was optimized using DFT calculations and a BLYP functional. The theoretical enantiomeric excess was calculated from the energy of each of the proposed complexes. The calculations were carried out considering different reaction solvents through the use of COSMO program. It was found that this simple model allows predicting the experimental values of both the sense of enantiodifferentiation and the enantiomeric excess with a good approximation. It was also able to predict the inversion of configuration when using the (S)-(+)-1-aminoindane as chiral modifier in polar solvents such as acetic acid and 2-propanol. - See more at: http://eurekaselect.com/119154#sthash.W69M4rz9.dpuf This paper deals with the computational modeling of the chiral modifier/substrate interaction for chiral modifiers studied in our laboratory, different from those conventionally used in enantioselective hydrogenation reactions. (S)- (+)-1-aminoindane and (R)-(-)-1-aminoindane were chosen as chiral modifiers and the selected substrates were methyl pyruvate, ethyl pyruvate and 1-ethyl-4,4-dimethyl-pyrrolidinae-2,3,5-trione. The geometry of each of the chiral modifier/substrate complexes was optimized using DFT calculations and a BLYP functional. The theoretical enantiomeric excess was calculated from the energy of each of the proposed complexes. The calculations were carried out considering different reaction solvents through the use of COSMO program. It was found that this simple model allows predicting the experimental values of both the sense of enantiodifferentiation and the enantiomeric excess with a good approximation. It was also able to predict the inversion of configuration when using the (S)-(+)-1-aminoindane as chiral modifier in polar solvents such as acetic acid and 2-propanol. - See more at: http://eurekaselect.com/119154#sthash.W69M4rz9.dpuf