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Titolo:
CONFORMATIONAL AND SOLVATION ASPECTS OF THE CHORISMATE-PREPHENATE REARRANGEMENT STUDIED BY AB-INITIO ELECTRONIC-STRUCTURE AND SIMULATION METHODS
Autore:
DAVIDSON MM; GUEST JM; CRAW JS; HILLIER IH; VINCENT MA;
Indirizzi:
UNIV MANCHESTER,DEPT CHEM,OXFORD RD MANCHESTER M13 9PL LANCS ENGLAND UNIV MANCHESTER,DEPT CHEM MANCHESTER M13 9PL LANCS ENGLAND
Titolo Testata:
Perkin transactions. 2
fascicolo: 7, , anno: 1997,
pagine: 1395 - 1400
SICI:
0300-9580(1997):7<1395:CASAOT>2.0.ZU;2-8
Fonte:
ISI
Lingua:
ENG
Soggetto:
ALLYL VINYL ETHER; CATALYZED CLAISEN REARRANGEMENT; TRANSITION-STATE; AQUEOUS ACCELERATION; BACILLUS-SUBTILIS; MUTASE; MECHANISM; ENZYME; ACID; STEREOCHEMISTRY;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Science Citation Index Expanded
Citazioni:
46
Recensione:
Indirizzi per estratti:
Citazione:
M.M. Davidson et al., "CONFORMATIONAL AND SOLVATION ASPECTS OF THE CHORISMATE-PREPHENATE REARRANGEMENT STUDIED BY AB-INITIO ELECTRONIC-STRUCTURE AND SIMULATION METHODS", Perkin transactions. 2, (7), 1997, pp. 1395-1400

Abstract

The effect of water on the energetics of the Claisen rearrangement ofchorismate to prephenate has been investigated with both a continuum model(PCM) and explicit solvation within a Monte Carlo (MC) free energy perturbation (FEP) treatment, Both models are surprisingly similar in their quantitative predictions, Solvation is shown to increase the conformational flexibility in the reactant by reducing the energy difference between the diequatorial and diaxial structures, and to lead to a considerable reduction in the barrier to the reaction, The estimate of the activation barrier, 22 kcal mol(-1),dagger is very close to theexperimental value of 24.5 kcal mol(-1). The implications of the various possible conformers on kinetic isotope effects are discussed.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 27/11/20 alle ore 15:34:52