Issue 19, 2015

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

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

Supplementary files

Article information

Article type
Paper
Submitted
13 Feb 2015
Accepted
12 Mar 2015
First published
13 Mar 2015
This article is Open Access
Creative Commons BY license

Org. Biomol. Chem., 2015,13, 5391-5398

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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