Reactions of oximate α-nucleophiles with esters:: Evidence from solvation effects for substantial decoupling of desolvation and bond formation

被引：64

作者：

Buncel, E ^{[1
]}

Cannes, C ^{[1
]}

Chatrousse, AP ^{[1
]}

Terrier, F ^{[1
]}

机构：

[1] Univ Versailles, SIRCOB, 45 Ave Etats Unis, F-78035 Versailles, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 30期

关键词：

D O I：

10.1021/ja020379k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This communication is concerned with deviations from linearity in Brønsted-type nucleophilicity plots as indicators of changes in transition-state structures, in particular as related to solvational effects. Increasing dimethyl sulfoxide (DMSO) content of DMSO-water mixtures removes the leveling off observed in Brønsted type plots of the reaction of p-nitrophenylacetate (PNPA) with oximate α-nucleophiles. This is interpreted as due to virtually complete decoupling between desolvation of the oxyanion nucleophile and bond formation in the rate-determining transition state (solvational imbalance). Copyright © 2002 American Chemical Society.

引用

页码：8766 / +

页数：2

共 37 条

[1] Determination of the pK(a), of ethyl acetate: Bronsted correlation for deprotonation of a simple oxygen ester in aqueous solution [J].

Amyes, TL ;

Richard, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (13) :3129-3141

[2] KINETICS OF IONIZATION OF 1,3-INDANDIONE IN ME2SO WATER MIXTURES - SOLVENT EFFECT ON INTRINSIC RATES AND BRONSTED COEFFICIENTS [J].

BERNASCONI, CF ;

PASCHALIS, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (11) :2969-2977

[3] NUCLEOPHILIC-ADDITION TO OLEFINS - KINETICS AND MECHANISM [J].

BERNASCONI, CF .

TETRAHEDRON, 1989, 45 (13) :4017-4090

[4]

BERNASCONI CF, 1992, ADV PHYS ORG CHEM, V27, P119

[5] EVIDENCE FOR A SINGLE TRANSITION-STATE IN THE TRANSFER OF THE PHOSPHORYL GROUP (-PO3-O-2-) TO NITROGEN NUCLEOPHILES FROM PYRIDINO-N-PHOSPHONATES [J].

BOURNE, N ;

WILLIAMS, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (24) :7591-7596

[6] SOLVENT-INDEPENDENT TRANSITION-STATE STRUCTURE FOR ACYL-TRANSFER REACTIONS - A NOVEL STRATEGY FOR CONSTRUCTION OF A BRONSTED CORRELATION [J].

BUNCEL, E ;

UM, IH ;

HOZ, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (03) :971-975

[7]

BUNCEL E, 1977, ADV PHYS ORG CHEM, V14, P133

[8] SULFUR DERIVATIVES OF 2-OXOPROPANAL OXIME AS REACTIVATORS OF ORGANOPHOSPHATE-INHIBITED ACETYLCHOLINESTERASE INVITRO - SYNTHESIS AND STRUCTURE-REACTIVITY RELATIONSHIPS [J].

DEGORRE, F ;

KIFFER, D ;

TERRIER, F .

JOURNAL OF MEDICINAL CHEMISTRY, 1988, 31 (04) :757-763

[9] ABSENCE OF AN ALPHA-EFFECT IN THE GAS-PHASE NUCLEOPHILIC REACTIONS OF HOO- [J].

DEPUY, CH ;

DELLA, EW ;

FILLEY, J ;

GRABOWSKI, JJ ;

BIERBAUM, VM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (08) :2481-2482

[10] ALPHA-EFFECT .5. KINETIC AND THERMODYNAMIC NATURE OF ALPHA-EFFECT FOR AMINE NUCLEOPHILES [J].

DIXON, JE ;

BRUICE, TC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (06) :2052-&

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