Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions...

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Autores principales: Carvalho, Alexandra T. P., O'Donoghue, AnnMarie C., Hodgson, David R. W., Kamerlin, Shina C. L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2015
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4425225/
https://www.ncbi.nlm.nih.gov/pubmed/25797408
http://dx.doi.org/10.1039/c5ob00309a
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author Carvalho, Alexandra T. P.
O'Donoghue, AnnMarie C.
Hodgson, David R. W.
Kamerlin, Shina C. L.
author_facet Carvalho, Alexandra T. P.
O'Donoghue, AnnMarie C.
Hodgson, David R. W.
Kamerlin, Shina C. L.
author_sort Carvalho, Alexandra T. P.
collection PubMed
description Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in S(N)2(P) mechanisms as the basis of these differences, rather than a change in mechanism.
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spelling pubmed-44252252015-05-13 Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge Carvalho, Alexandra T. P. O'Donoghue, AnnMarie C. Hodgson, David R. W. Kamerlin, Shina C. L. Org Biomol Chem Chemistry Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in S(N)2(P) mechanisms as the basis of these differences, rather than a change in mechanism. Royal Society of Chemistry 2015-05-21 2015-03-23 /pmc/articles/PMC4425225/ /pubmed/25797408 http://dx.doi.org/10.1039/c5ob00309a Text en This journal is © The Royal Society of Chemistry 2015 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
Carvalho, Alexandra T. P.
O'Donoghue, AnnMarie C.
Hodgson, David R. W.
Kamerlin, Shina C. L.
Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title_full Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title_fullStr Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title_full_unstemmed Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title_short Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
title_sort understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4425225/
https://www.ncbi.nlm.nih.gov/pubmed/25797408
http://dx.doi.org/10.1039/c5ob00309a
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