A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate
Autor(a) principal: | |
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Data de Publicação: | 2001 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Brazilian Journal of Chemical Engineering |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66322001000300008 |
Resumo: | Hydrogenation of methyl pyruvate on a palladium or platinum surface in the presence of cinchona alkaloids leads to a high degree of enantiodifferentiation. In the present study, the semiempirical AM1 and PM3 methods are employed to perform a detailed analysis of the conformational behavior of cinchonidine and to study its interaction with methyl pyruvate. Nine different minima were located on the potential energy surface for cinchonidine by both the AM1 and the PM3 methods. Some barriers to interconversion between them are relatively high; however, it is always possible to connect two minima through barriers lower than 3.0 kcal/mol so most of the minima can interact with the substrate. The interaction between cinchonidine and methyl pyruvate was calculated by placing methyl pyruvate near the cinchonidine molecule in different orientations and optimizing the final complex. The calculated interaction energy is lower than 3.5 kcal/moland is predominantly due to van der Waals noncovalent interactions. An analysis of the structure of possible pro-R and pro-S complexes indicates that interaction between cinchonidine and methyl pyruvate alone is not enough to induce enantiodifferentiation. |
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Brazilian Journal of Chemical Engineering |
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A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvateheterogeneousenantioselectivecatalysismechanismscalculationsmolecular modellingHydrogenation of methyl pyruvate on a palladium or platinum surface in the presence of cinchona alkaloids leads to a high degree of enantiodifferentiation. In the present study, the semiempirical AM1 and PM3 methods are employed to perform a detailed analysis of the conformational behavior of cinchonidine and to study its interaction with methyl pyruvate. Nine different minima were located on the potential energy surface for cinchonidine by both the AM1 and the PM3 methods. Some barriers to interconversion between them are relatively high; however, it is always possible to connect two minima through barriers lower than 3.0 kcal/mol so most of the minima can interact with the substrate. The interaction between cinchonidine and methyl pyruvate was calculated by placing methyl pyruvate near the cinchonidine molecule in different orientations and optimizing the final complex. The calculated interaction energy is lower than 3.5 kcal/moland is predominantly due to van der Waals noncovalent interactions. An analysis of the structure of possible pro-R and pro-S complexes indicates that interaction between cinchonidine and methyl pyruvate alone is not enough to induce enantiodifferentiation.Brazilian Society of Chemical Engineering2001-09-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66322001000300008Brazilian Journal of Chemical Engineering v.18 n.3 2001reponame:Brazilian Journal of Chemical Engineeringinstname:Associação Brasileira de Engenharia Química (ABEQ)instacron:ABEQ10.1590/S0104-66322001000300008info:eu-repo/semantics/openAccessAranda,D.A.G.Carneiro,J.W.M.Oliveira,C.S.B.Passos,F.B.Souza,P.R.N.Antunes,O.A.C.eng2001-10-10T00:00:00Zoai:scielo:S0104-66322001000300008Revistahttps://www.scielo.br/j/bjce/https://old.scielo.br/oai/scielo-oai.phprgiudici@usp.br||rgiudici@usp.br1678-43830104-6632opendoar:2001-10-10T00:00Brazilian Journal of Chemical Engineering - Associação Brasileira de Engenharia Química (ABEQ)false |
dc.title.none.fl_str_mv |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
title |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
spellingShingle |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate Aranda,D.A.G. heterogeneous enantioselective catalysis mechanisms calculations molecular modelling |
title_short |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
title_full |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
title_fullStr |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
title_full_unstemmed |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
title_sort |
A semiempirical study of the conformational behavior of cinchonidine and its interaction with methyl pyruvate |
author |
Aranda,D.A.G. |
author_facet |
Aranda,D.A.G. Carneiro,J.W.M. Oliveira,C.S.B. Passos,F.B. Souza,P.R.N. Antunes,O.A.C. |
author_role |
author |
author2 |
Carneiro,J.W.M. Oliveira,C.S.B. Passos,F.B. Souza,P.R.N. Antunes,O.A.C. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Aranda,D.A.G. Carneiro,J.W.M. Oliveira,C.S.B. Passos,F.B. Souza,P.R.N. Antunes,O.A.C. |
dc.subject.por.fl_str_mv |
heterogeneous enantioselective catalysis mechanisms calculations molecular modelling |
topic |
heterogeneous enantioselective catalysis mechanisms calculations molecular modelling |
description |
Hydrogenation of methyl pyruvate on a palladium or platinum surface in the presence of cinchona alkaloids leads to a high degree of enantiodifferentiation. In the present study, the semiempirical AM1 and PM3 methods are employed to perform a detailed analysis of the conformational behavior of cinchonidine and to study its interaction with methyl pyruvate. Nine different minima were located on the potential energy surface for cinchonidine by both the AM1 and the PM3 methods. Some barriers to interconversion between them are relatively high; however, it is always possible to connect two minima through barriers lower than 3.0 kcal/mol so most of the minima can interact with the substrate. The interaction between cinchonidine and methyl pyruvate was calculated by placing methyl pyruvate near the cinchonidine molecule in different orientations and optimizing the final complex. The calculated interaction energy is lower than 3.5 kcal/moland is predominantly due to van der Waals noncovalent interactions. An analysis of the structure of possible pro-R and pro-S complexes indicates that interaction between cinchonidine and methyl pyruvate alone is not enough to induce enantiodifferentiation. |
publishDate |
2001 |
dc.date.none.fl_str_mv |
2001-09-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66322001000300008 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66322001000300008 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1590/S0104-66322001000300008 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Brazilian Society of Chemical Engineering |
publisher.none.fl_str_mv |
Brazilian Society of Chemical Engineering |
dc.source.none.fl_str_mv |
Brazilian Journal of Chemical Engineering v.18 n.3 2001 reponame:Brazilian Journal of Chemical Engineering instname:Associação Brasileira de Engenharia Química (ABEQ) instacron:ABEQ |
instname_str |
Associação Brasileira de Engenharia Química (ABEQ) |
instacron_str |
ABEQ |
institution |
ABEQ |
reponame_str |
Brazilian Journal of Chemical Engineering |
collection |
Brazilian Journal of Chemical Engineering |
repository.name.fl_str_mv |
Brazilian Journal of Chemical Engineering - Associação Brasileira de Engenharia Química (ABEQ) |
repository.mail.fl_str_mv |
rgiudici@usp.br||rgiudici@usp.br |
_version_ |
1754213171098288128 |