Structure and reactivity of phosphate diesters. Dependence on the nonleaving group

Autor:	Anthony J. Kirby, Faruk Nome, Bruno S. Souza
Rok vydání:	2015
Předmět:	Bond length Hydrolysis chemistry.chemical_compound chemistry Organic Chemistry Leaving group Organic chemistry Molecule General Chemistry Phosphate Medicinal chemistry Catalysis Lower temperature
Zdroj:	Canadian Journal of Chemistry. 93:422-427
ISSN:	1480-3291 0008-4042
DOI:	10.1139/cjc-2014-0358
Popis:	The hydrolytic reactivity of simple phosphate diesters with very good leaving groups is known to be practically independent of the nonleaving group at 100 °C. Calculations on the (too slow to measure) hydrolysis at 25 °C of a series of p-nitrophenyl diesters ROPO2––OpNP with a wide range of nonleaving group OR indicate a small but significant effect at the lower temperature, making the R = methyl ester the most reactive. This is in the opposite sense to the much larger effect observed for the reactions of triesters and consistent with a reaction driven primarily by leaving group departure. The calculations use a continuum model with up to four discrete water molecules: two or three waters give the best results.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::eafad603eaeb9ebbee304af4cb9af440 https://doi.org/10.1139/cjc-2014-0358 Zobrazit plný text záznamu Plný text ve formátu PDF