Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones
- Autores
- Ruggera, José Fernando; Gázquez, Ayelén; Pis Diez, Reinaldo; Casella, Mónica Laura
- Año de publicación
- 2014
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- 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-pyrrolidin-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.
Fil: Ruggera, José Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Gázquez, Ayelén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina
Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Casella, Mónica Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina - Materia
-
Theoretical Modeling
Enantioselectivity
Dft
Hydrogenation
Chiral Modifiers
Aminoindane - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/22391
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Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketonesRuggera, José FernandoGázquez, AyelénPis Diez, ReinaldoCasella, Mónica LauraTheoretical ModelingEnantioselectivityDftHydrogenationChiral ModifiersAminoindanehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This 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-pyrrolidin-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.Fil: Ruggera, José Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Gázquez, Ayelén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Casella, Mónica Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaBentham Science Publishers2014-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/22391Ruggera, José Fernando; Gázquez, Ayelén; Pis Diez, Reinaldo; Casella, Mónica Laura; Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones; Bentham Science Publishers; Current Catalysis; 3; 2; 3-2014; 213-2192211-54472211-5455CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.eurekaselect.com/119154info:eu-repo/semantics/altIdentifier/doi/10.2174/2211544702666131224231309info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:14:47Zoai:ri.conicet.gov.ar:11336/22391instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:14:47.982CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
title |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
spellingShingle |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones Ruggera, José Fernando Theoretical Modeling Enantioselectivity Dft Hydrogenation Chiral Modifiers Aminoindane |
title_short |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
title_full |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
title_fullStr |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
title_full_unstemmed |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
title_sort |
Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones |
dc.creator.none.fl_str_mv |
Ruggera, José Fernando Gázquez, Ayelén Pis Diez, Reinaldo Casella, Mónica Laura |
author |
Ruggera, José Fernando |
author_facet |
Ruggera, José Fernando Gázquez, Ayelén Pis Diez, Reinaldo Casella, Mónica Laura |
author_role |
author |
author2 |
Gázquez, Ayelén Pis Diez, Reinaldo Casella, Mónica Laura |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
Theoretical Modeling Enantioselectivity Dft Hydrogenation Chiral Modifiers Aminoindane |
topic |
Theoretical Modeling Enantioselectivity Dft Hydrogenation Chiral Modifiers Aminoindane |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
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-pyrrolidin-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. Fil: Ruggera, José Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Gázquez, Ayelén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Pis Diez, Reinaldo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina Fil: Casella, Mónica Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina |
description |
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-pyrrolidin-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. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-03 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/22391 Ruggera, José Fernando; Gázquez, Ayelén; Pis Diez, Reinaldo; Casella, Mónica Laura; Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones; Bentham Science Publishers; Current Catalysis; 3; 2; 3-2014; 213-219 2211-5447 2211-5455 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/22391 |
identifier_str_mv |
Ruggera, José Fernando; Gázquez, Ayelén; Pis Diez, Reinaldo; Casella, Mónica Laura; Theoretical modeling of the interaction chiral modifier/substrate as a key step in the enantioselective hydrogenation of α-ketoesters and vicinal diketones; Bentham Science Publishers; Current Catalysis; 3; 2; 3-2014; 213-219 2211-5447 2211-5455 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/http://www.eurekaselect.com/119154 info:eu-repo/semantics/altIdentifier/doi/10.2174/2211544702666131224231309 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf application/pdf application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Bentham Science Publishers |
publisher.none.fl_str_mv |
Bentham Science Publishers |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844614078897586176 |
score |
13.070432 |