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The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations

The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K(12)Ga(4)L(6) tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelato...

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Autores principales: Hart-Cooper, William M., Zhao, Chen, Triano, Rebecca M., Yaghoubi, Parastou, Ozores, Haxel Lionel, Burford, Kristen N., Toste, F. Dean, Bergman, Robert G., Raymond, Kenneth N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811099/
https://www.ncbi.nlm.nih.gov/pubmed/29560226
http://dx.doi.org/10.1039/c4sc02735c
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author Hart-Cooper, William M.
Zhao, Chen
Triano, Rebecca M.
Yaghoubi, Parastou
Ozores, Haxel Lionel
Burford, Kristen N.
Toste, F. Dean
Bergman, Robert G.
Raymond, Kenneth N.
author_facet Hart-Cooper, William M.
Zhao, Chen
Triano, Rebecca M.
Yaghoubi, Parastou
Ozores, Haxel Lionel
Burford, Kristen N.
Toste, F. Dean
Bergman, Robert G.
Raymond, Kenneth N.
author_sort Hart-Cooper, William M.
collection PubMed
description The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K(12)Ga(4)L(6) tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 10(5), which numbers among the largest magnitudes of transition state stabilization measured with a synthetic host-catalyst. Host/guest size effects were observed to play an important role in host-mediated enantioselectivity.
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spelling pubmed-58110992018-03-20 The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations Hart-Cooper, William M. Zhao, Chen Triano, Rebecca M. Yaghoubi, Parastou Ozores, Haxel Lionel Burford, Kristen N. Toste, F. Dean Bergman, Robert G. Raymond, Kenneth N. Chem Sci Chemistry The effect of host structure on the selectivity and mechanism of intramolecular Prins reactions is evaluated using K(12)Ga(4)L(6) tetrahedral catalysts. The host structure was varied by modifying the structure of the chelating moieties and the size of the aromatic spacers. While variation in chelator substituents was generally observed to affect changes in rate but not selectivity, changing the host spacer afforded differences in efficiency and product diastereoselectivity. An extremely high number of turnovers (up to 840) was observed. Maximum rate accelerations were measured to be on the order of 10(5), which numbers among the largest magnitudes of transition state stabilization measured with a synthetic host-catalyst. Host/guest size effects were observed to play an important role in host-mediated enantioselectivity. Royal Society of Chemistry 2015-02-01 2014-11-28 /pmc/articles/PMC5811099/ /pubmed/29560226 http://dx.doi.org/10.1039/c4sc02735c Text en This journal is © The Royal Society of Chemistry 2014 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Hart-Cooper, William M.
Zhao, Chen
Triano, Rebecca M.
Yaghoubi, Parastou
Ozores, Haxel Lionel
Burford, Kristen N.
Toste, F. Dean
Bergman, Robert G.
Raymond, Kenneth N.
The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title_full The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title_fullStr The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title_full_unstemmed The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title_short The effect of host structure on the selectivity and mechanism of supramolecular catalysis of Prins cyclizations
title_sort effect of host structure on the selectivity and mechanism of supramolecular catalysis of prins cyclizations
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5811099/
https://www.ncbi.nlm.nih.gov/pubmed/29560226
http://dx.doi.org/10.1039/c4sc02735c
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