Isotope effects and the distinction between synchronous, asynchronous, and stepwise Diels-Alder reactions

被引：85

作者：

Singleton, DA ^{[1
]}

Schulmeier, BE ^{[1
]}

Hang, C ^{[1
]}

Thomas, AA ^{[1
]}

Leung, SW ^{[1
]}

Merrigan, SR ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77842 USA

来源：

TETRAHEDRON | 2001年 / 57卷 / 24期

基金：

美国国家卫生研究院;

关键词：

Diels-Alder reaction; isotope effect; asynchronous transition state;

D O I：

10.1016/S0040-4020(01)00354-4

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A. variety of symmetrical or nearly symmetrical Diels-Alder reactions are studied by a combination of experimental isotope effects, theoretical calculations, and rate observations. Becke3LYP calculations predicted highly asynchronous transition structures for Diels-Alder reactions of bis(boryl)acetylenes, dialkyl acetylenedicarboxylates, triazolinediones, and dialkyl maleates. Rate observations and kinetic isotope effects are consistent with these predictions, though the experimental support for the calculated structures is notably ambiguous in some cases. A concerted mechanism is supported for the retro-Diels-Alder reaction of norbornene. Overall, Diels-Alder reactions appear to be only very weakly biased toward synchronous transition states. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：5149 / 5160

页数：12

共 54 条

[31] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

[32] Reactions of alkynyldihaloboranes with 1,3-dienes. 1,4-alkynylborations and stepwise Diels-Alder reactions [J].

Leung, SW ;

Singleton, DA .

JOURNAL OF ORGANIC CHEMISTRY, 1997, 62 (07) :1955-1960

[33] DIELS-ALDER DIMERIZATION OF 1,3-BUTADIENE - AN AB-INITIO CASSCF STUDY OF THE CONCERTED AND STEPWISE MECHANISMS AND BUTADIENE ETHYLENE REVISITED [J].

LI, Y ;

HOUK, KN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (16) :7478-7485

[34] TRANSITION STRUCTURES OF THE DIELS-ALDER REACTION OF BUTADIENE WITH ACROLEIN [J].

LONCHARICH, RJ ;

BROWN, FK ;

HOUK, KN .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (05) :1129-1134

[35] HETERO-DIELS-ALDER REACTION TRANSITION STRUCTURES - REACTIVITY, STEREOSELECTIVITY, CATALYSIS, SOLVENT EFFECTS, AND THE EXO-LONE-PAIR EFFECT [J].

MCCARRICK, MA ;

WU, YD ;

HOUK, KN .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (12) :3330-3343

[36] Reinvestigation of the isotope effects for the Claisen and aromatic Claisen rearrangements: The nature of the Claisen transition states [J].

Meyer, MP ;

DelMonte, AJ ;

Singleton, DA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (47) :10865-10874

[37] REGIOSELECTIVE PREPARATION OF CYCLOHEXADIENES OR AROMATIC NITRO-COMPOUNDS BY DIELS-ALDER REACTIONS OF BETA-SULFONYLNITROOLEFINS OR BETA-SULFINYLNITROETHYLENE [J].

ONO, N ;

KAMIMURA, A ;

KAJI, A .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (02) :251-258

[38]

Parr R. G., 1989, Density Functional Theory of Atoms and Molecules

[39] Theoretical analysis of concerted and stepwise mechanisms of Diels-Alder reaction between butadiene and ethylene [J].

Sakai, S .

JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (05) :922-927

[40] MECHANISTIC ASPECTS OF DIELS-ALDER REACTIONS - A CRITICAL SURVEY [J].

SAUER, J ;

SUSTMANN, R .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1980, 19 (10) :779-807

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