Hydrolysis of phosphonoformate triesters: rate acceleration of a millionfold in nucleophilic substitution at phosphorus

Autor:	E. S. Krol, Gregory R. J. Thatcher
Rok vydání:	1993
Předmět:	Hydrolysis chemistry.chemical_compound Reaction rate constant Nucleophile chemistry Intramolecular force Nucleophilic substitution Organic chemistry Buffer solution Medicinal chemistry Bond cleavage Catalysis
Zdroj:	Journal of the Chemical Society, Perkin Transactions 2. :793
ISSN:	1364-5471 0300-9580
DOI:	10.1039/p29930000793
Popis:	The base-catalysed hydrolysis of triesters of phosphonoformic acid via P–O bond cleavage proceeds at rates at least 104 times greater than diethyl difluoromethylphosphonate and 106 times greater than diphenyl methylphosphonate. Buffer catalysis and isotope labelling studies suggest the mechanism of rate acceleration by the ethoxycarbonyl group to involve either intramolecular nucleophilic catalyses via a three-membered ring or stereoelectronic assistance, both of which are unprecedented.
Databáze:	OpenAIRE
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