Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction

This study represents the first example where the accuracy of different combinations of density functional theory (DFT) methods and basis sets have been compared in squaramide catalysis. After an optimization process of the precision obtained and the computational time required in the computational...

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Autores: Alegre-Requena, Juan V., Marqués-López, Eugenia, Herrera, Raquel P.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/184844
Acceso en línea:http://hdl.handle.net/10261/184844
Access Level:acceso abierto
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spelling Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reactionAlegre-Requena, Juan V.Marqués-López, EugeniaHerrera, Raquel P.This study represents the first example where the accuracy of different combinations of density functional theory (DFT) methods and basis sets have been compared in squaramide catalysis. After an optimization process of the precision obtained and the computational time required in the computational calculations, highly precise results were achieved compared to the experimental outcomes while requiring the least amount of time possible. Here, we have explored computationally and experimentally the mechanism of the squaramide‐catalyzed Henry reaction. This is a complex reaction of about 100 atoms and a great number of diverse non‐covalent interactions. Moreover, this research is one of the scarce examples where the organocatalyst acts in a trifunctional manner and is the first investigation in which a trifunctional squaramide catalyst has been employed. Functional ωB97X‐D showed the best results when used with different versions of the 6‐311 basis sets, leading to highly accurate calculations of the outcomes of the Henry reaction when using nine aldehydes with different structural characteristics. Furthermore, in these relatively large systems, the use of a split‐valence triple‐zeta basis set saves a large amount of time compared with using larger basis sets that are sometimes employed in organocatalytic studies, such as the TZV and Def2TZV basis set families.We thank the Government of Aragon DGA (Research Group E‐104) for financial support of our research. All the calculations were performed in the Trueno cluster facility of SGAI‐CSIC. J.V.A.‐R. thanks the DGA for a predoctoral contract. The authors thank Leah C. Weatherman for her help during the text editing process. J.V.A.‐R. thanks Dr. Robert S. Paton (CRL, University of Oxford) for his support with the QHA script.Peer reviewedWiley-VCHGobierno de AragónUniversity of OxfordDiputación General de AragónConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]201920192017info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/184844reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1002/chem.201702841Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1848442026-05-22T06:33:51Z
dc.title.none.fl_str_mv Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
title Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
spellingShingle Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
Alegre-Requena, Juan V.
title_short Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
title_full Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
title_fullStr Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
title_full_unstemmed Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
title_sort Optimizing accuracy and computational cost in theoretical squaramide catalysis: the Henry reaction
dc.creator.none.fl_str_mv Alegre-Requena, Juan V.
Marqués-López, Eugenia
Herrera, Raquel P.
author Alegre-Requena, Juan V.
author_facet Alegre-Requena, Juan V.
Marqués-López, Eugenia
Herrera, Raquel P.
author_role author
author2 Marqués-López, Eugenia
Herrera, Raquel P.
author2_role author
author
dc.contributor.none.fl_str_mv Gobierno de Aragón
University of Oxford
Diputación General de Aragón
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description This study represents the first example where the accuracy of different combinations of density functional theory (DFT) methods and basis sets have been compared in squaramide catalysis. After an optimization process of the precision obtained and the computational time required in the computational calculations, highly precise results were achieved compared to the experimental outcomes while requiring the least amount of time possible. Here, we have explored computationally and experimentally the mechanism of the squaramide‐catalyzed Henry reaction. This is a complex reaction of about 100 atoms and a great number of diverse non‐covalent interactions. Moreover, this research is one of the scarce examples where the organocatalyst acts in a trifunctional manner and is the first investigation in which a trifunctional squaramide catalyst has been employed. Functional ωB97X‐D showed the best results when used with different versions of the 6‐311 basis sets, leading to highly accurate calculations of the outcomes of the Henry reaction when using nine aldehydes with different structural characteristics. Furthermore, in these relatively large systems, the use of a split‐valence triple‐zeta basis set saves a large amount of time compared with using larger basis sets that are sometimes employed in organocatalytic studies, such as the TZV and Def2TZV basis set families.
publishDate 2017
dc.date.none.fl_str_mv 2017
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
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status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/184844
url http://hdl.handle.net/10261/184844
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1002/chem.201702841
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
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