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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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Publication details

The article was received on 13 Feb 2015, accepted on 12 Mar 2015 and first published on 13 Mar 2015


Article type: Paper
DOI: 10.1039/C5OB00309A
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Citation: Org. Biomol. Chem., 2015,13, 5391-5398
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    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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