Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge

Carvalho, A.; O’Donoghue, A.C.; Hodgson, D.R.W.; Kamerlin, S.C.L.

doi:10.1039/c5ob00309a

Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge

Carvalho, A.; O’Donoghue, A.C.; Hodgson, D.R.W.; Kamerlin, S.C.L.

Authors

A. Carvalho

Professor Ann O'Donoghue annmarie.odonoghue@durham.ac.uk
Professor

Professor David Hodgson d.r.w.hodgson@durham.ac.uk
Professor

S.C.L. 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.

Citation

Carvalho, A., O’Donoghue, A., Hodgson, D., & Kamerlin, S. (2015). Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge. Organic and Biomolecular Chemistry, 13(19), 5391-5398. https://doi.org/10.1039/c5ob00309a

Journal Article Type	Article
Acceptance Date	Feb 25, 2015
Publication Date	May 21, 2015
Deposit Date	Apr 8, 2015
Publicly Available Date	Apr 28, 2015
Journal	Organic and Biomolecular Chemistry
Print ISSN	1477-0520
Electronic ISSN	1477-0539
Publisher	Royal Society of Chemistry
Peer Reviewed	Peer Reviewed
Volume	13
Issue	19
Pages	5391-5398
DOI	https://doi.org/10.1039/c5ob00309a