Experimental Diels-Alder Reactivities of Cycloalkenones and Cyclic Dienes Explained through Transition-State Distortion Energies

被引：120

作者：

Paton, Robert S. ^{[1
]}

Kim, Seonah ^{[2
]}

Ross, Audrey G. ^{[3
]}

Danishefsky, Samuel J. ^{[3
]}

Houk, K. N. ^{[2
]}

机构：

[1] Univ Oxford, Chem Res Lab, Oxford OX1 3TA, England

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[3] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 44期

基金：

美国国家科学基金会;

关键词：

cycloaddition; Diels-Alder reaction; polycycles; stereoselectivity; strained molecules; CYCLOADDITIONS; DISTORTION/INTERACTION;

D O I：

10.1002/anie.201103998

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Quantum chemical calculations are used to investigate the experimentally measured reactivities of cyclic dienes and cycloalkenones in the Diels-Alder reaction. The interaction energies (red) are nearly constant; differences arise in changes in distortion energies of both dienophile (blue) and diene (green; see picture, Ea=activation energy; values in kcal mol-1). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

收藏

页码：10366 / 10368

页数：3

相关论文

共 24 条

[11]

JENCKS WP, 1985, CHEM REV, V85, P511, DOI 10.1021/cr00070a001

[12] GENERAL ACID-BASE CATALYSIS OF COMPLEX REACTIONS IN WATER [J].

JENCKS, WP .

CHEMICAL REVIEWS, 1972, 72 (06) :705-&

[13] Rapid access to tricyclic systems: Highly endoselective Diels-Alder reaction of cycloalkenones with cyclic dienes under microwave irradiation [J].

Karthikeyan, M ;

Kamakshi, R ;

Sridar, V ;

Reddy, BSR .

SYNTHETIC COMMUNICATIONS, 2003, 33 (24) :4199-4204

[14] Diels-Alder Exo Selectivity in Terminal-Substituted Dienes and Dienophiles: Experimental Discoveries and Computational Explanations [J].

Lam, Yu-hong ;

Cheong, Paul Ha-Yeon ;

Mata, Jose M. Blasco ;

Stanway, Steven J. ;

Gouverneur, Veronique ;

Houk, K. N. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (05) :1947-1957

[15] Cyclobutenone as a Highly Reactive Dienophile: Expanding Upon Diels-Alder Paradigms [J].

Li, Xiaohua ;

Danishefsky, Samuel J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (32) :11004-11005

[16] Origins of Stereoselectivity in the trans Diels-Alder Paradigm [J].

Paton, Robert S. ;

Mackey, Joel L. ;

Kim, Woo Han ;

Lee, Jun Hee ;

Danishefsky, Samuel J. ;

Houk, K. N. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (27) :9335-9340

[17]

Pieniazek S., 2006, Angew. Chem, V118, P1470

[18]

Pieniazek S.N., 2008, Angew. Chem. Int. Ed, V120, P7860, DOI DOI 10.1002/ANGE.200801843

[19] The origin of the halogen effect on reactivity and reversibility of Diels-Alder cycloadditions involving furan [J].

Pieniazek, SN ;

Houk, KN .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (09) :1442-1445

[20] Sources of error in DFT computations of C-C bond formation thermochemistries:: π→σ transformations and error cancellation by DFT methods [J].

Pieniazek, Susan N. ;

Clemente, Fernando R. ;

Houk, Kendall N. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (40) :7746-7749