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

E. S. Krol; Gregory R.J. Thatcher

doi:10.1039/p29930000793

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

E. S. Krol
, Gregory R.J. Thatcher

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	793-794
Number of pages	2
Journal	Journal of the Chemical Society, Perkin Transactions 2
Issue number	5
DOIs	https://doi.org/10.1039/p29930000793
State	Published - 1993
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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10.1039/p29930000793

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title = "Hydrolysis of phosphonoformate triesters: Rate acceleration of a millionfold in nucleophilic substitution at phosphorus",

abstract = "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.",

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year = "1993",

doi = "10.1039/p29930000793",

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publisher = "Chemical Society",

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AU - Krol, E. S.

AU - Thatcher, Gregory R.J.

PY - 1993

Y1 - 1993

N2 - 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.

AB - 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.

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U2 - 10.1039/p29930000793

DO - 10.1039/p29930000793

M3 - Article

AN - SCOPUS:37049068350

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JO - Journal of the Chemical Society, Perkin Transactions 2

JF - Journal of the Chemical Society, Perkin Transactions 2

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

Abstract

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