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Issue 19, 2015
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Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge

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Abstract

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 SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism.

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

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Supplementary files

Article information


Submitted
13 Feb 2015
Accepted
12 Mar 2015
First published
13 Mar 2015

This article is Open Access

Org. Biomol. Chem., 2015,13, 5391-5398
Article type
Paper
Author version available

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

A. T. P. Carvalho, A. C. O'Donoghue, D. R. W. Hodgson and S. C. L. Kamerlin, Org. Biomol. Chem., 2015, 13, 5391
DOI: 10.1039/C5OB00309A

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