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

Organic & Biomolecular Chemistry
Alexandra T P CarvalhoShina Caroline Lynn Kamerlin

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.

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Citations

Feb 22, 2017·The Journal of Organic Chemistry·Mónica Álvarez-PérezMiguel A Sierra

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