Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process

A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an exper...

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Autores principales: Han, Xiao, Lee, Richmond, Chen, Tao, Luo, Jie, Lu, Yixin, Huang, Kuo-Wei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2013
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3757351/
https://www.ncbi.nlm.nih.gov/pubmed/23990028
http://dx.doi.org/10.1038/srep02557
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author Han, Xiao
Lee, Richmond
Chen, Tao
Luo, Jie
Lu, Yixin
Huang, Kuo-Wei
author_facet Han, Xiao
Lee, Richmond
Chen, Tao
Luo, Jie
Lu, Yixin
Huang, Kuo-Wei
author_sort Han, Xiao
collection PubMed
description A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity.
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spelling pubmed-37573512013-08-30 Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process Han, Xiao Lee, Richmond Chen, Tao Luo, Jie Lu, Yixin Huang, Kuo-Wei Sci Rep Article A combined kinetic and computational study on our tryptophan-based bifunctional thiourea catalyzed asymmetric Mannich reactions reveals an apparent negative activation enthalpy. The formation of the pre-transition state complex has been unambiguously confirmed and these observations provide an experimental support for the formation of multiple hydrogen bonding network between the substrates and the catalyst. Such interactions allow the creation of a binding cavity, a key factor to install high enantioselectivity. Nature Publishing Group 2013-08-30 /pmc/articles/PMC3757351/ /pubmed/23990028 http://dx.doi.org/10.1038/srep02557 Text en Copyright © 2013, Macmillan Publishers Limited. All rights reserved http://creativecommons.org/licenses/by-nc-nd/3.0/ This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-nd/3.0/
spellingShingle Article
Han, Xiao
Lee, Richmond
Chen, Tao
Luo, Jie
Lu, Yixin
Huang, Kuo-Wei
Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title_full Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title_fullStr Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title_full_unstemmed Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title_short Kinetic Evidence of an Apparent Negative Activation Enthalpy in an Organocatalytic Process
title_sort kinetic evidence of an apparent negative activation enthalpy in an organocatalytic process
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3757351/
https://www.ncbi.nlm.nih.gov/pubmed/23990028
http://dx.doi.org/10.1038/srep02557
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