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

Carvalho AT, O'Donoghue AC, Hodgson DR, Kamerlin SC

Org. Biomol. Chem. 13 (19) 5391-5398 [2015-05-21; online 2015-03-24]

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.

Affiliated researcher

PubMed 25797408

DOI 10.1039/c5ob00309a

Crossref 10.1039/c5ob00309a

pmc: PMC4425225

Publications 9.5.0