How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins

Chloroperoxidase-catalyzed enantiospecific epoxidations of olefins are of significant biotechnological interest. Typical enantiomeric excesses are in the range of 66%–97% and translate into free energy differences on the order of 1 kcal/mol. These differences are generally attributed to the effect o...

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Autores principales: Morozov, Alexander N., Chatfield, David C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2016
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5000694/
https://www.ncbi.nlm.nih.gov/pubmed/27517911
http://dx.doi.org/10.3390/ijms17081297
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author Morozov, Alexander N.
Chatfield, David C.
author_facet Morozov, Alexander N.
Chatfield, David C.
author_sort Morozov, Alexander N.
collection PubMed
description Chloroperoxidase-catalyzed enantiospecific epoxidations of olefins are of significant biotechnological interest. Typical enantiomeric excesses are in the range of 66%–97% and translate into free energy differences on the order of 1 kcal/mol. These differences are generally attributed to the effect of the distal pocket. In this paper, we show that the influence of the proximal pocket on the electron transfer mechanism in the rate-limiting event may be just as significant for a quantitatively accurate account of the experimentally-measured enantiospecificities.
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spelling pubmed-50006942016-09-01 How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins Morozov, Alexander N. Chatfield, David C. Int J Mol Sci Article Chloroperoxidase-catalyzed enantiospecific epoxidations of olefins are of significant biotechnological interest. Typical enantiomeric excesses are in the range of 66%–97% and translate into free energy differences on the order of 1 kcal/mol. These differences are generally attributed to the effect of the distal pocket. In this paper, we show that the influence of the proximal pocket on the electron transfer mechanism in the rate-limiting event may be just as significant for a quantitatively accurate account of the experimentally-measured enantiospecificities. MDPI 2016-08-09 /pmc/articles/PMC5000694/ /pubmed/27517911 http://dx.doi.org/10.3390/ijms17081297 Text en © 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Morozov, Alexander N.
Chatfield, David C.
How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title_full How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title_fullStr How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title_full_unstemmed How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title_short How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins
title_sort how the proximal pocket may influence the enantiospecificities of chloroperoxidase-catalyzed epoxidations of olefins
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5000694/
https://www.ncbi.nlm.nih.gov/pubmed/27517911
http://dx.doi.org/10.3390/ijms17081297
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