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

被引：119

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

页码：10366 / 10368

页数：3

共 49 条

[1] THE INFLUENCE OF THE CYCLIC PRODUCT STRUCTURE ON THE DIELS-ALDER TRANSITION-STATE
BURKE, LA
THEORETICA CHIMICA ACTA, 1985, 68 (02): : 101 - 105
[2] TRANSITION-STATE OF DIELS-ALDER REACTION
BASILEVSKY, MV
SHAMOV, AG
TIKHOMIROV, VA
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (05) : 1369 - 1372
[3] STEREOCHEMISTRY OF THE TRANSITION-STATE IN DIELS-ALDER REACTIONS
ELYANOV, BS
SHAKHOVA, SK
POLKOVNIKOV, BD
RAR, LA
BULLETIN OF THE ACADEMY OF SCIENCES OF THE USSR DIVISION OF CHEMICAL SCIENCE, 1979, 28 (11): : 2472 - 2473
[4] DESIGN AND SYNTHESIS OF TRANSITION-STATE ANALOGS FOR THE DIELS-ALDER REACTION
NOWICK, JS
ARORA, PS
FAMULOK, M
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1995, 209 : 110 - ORGN
[5] A TRANSITION-STATE FMO APPROACH FOR PREDICTION OF THE REGIOSELECTIVITY OF THE DIELS-ALDER REACTION
ALSTON, PV
OTTENBRITE, RM
GUNER, OF
SHILLADY, DD
TETRAHEDRON, 1986, 42 (16) : 4403 - 4408
[6] ABINITIO CS TRANSITION-STATE FOR THE DIELS-ALDER REACTION OF ACETYLENE AND BUTADIENE
COXON, JM
GRICE, ST
MACLAGAN, RGAR
MCDONALD, DQ
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (12): : 3804 - 3807
[7] ENRICHMENT FOR RNA MOLECULES THAT BIND A DIELS-ALDER TRANSITION-STATE ANALOG
MORRIS, KN
TARASOW, TM
JULIN, CM
SIMONS, SL
HILVERT, D
GOLD, L
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1994, 91 (26) : 13028 - 13032
[8] Rapid access to tricyclic systems: Highly endoselective Diels-Alder reaction of cycloalkenones with cyclic dienes under microwave irradiation
Karthikeyan, M
Kamakshi, R
Sridar, V
Reddy, BSR
SYNTHETIC COMMUNICATIONS, 2003, 33 (24) : 4199 - 4204
[9] Transition State Distortion Energies Correlate with Activation Energies of 1,4-Dihydrogenations and Diels-Alder Cycloadditions of Aromatic Molecules
Hayden, Amy E.
Houk, K. N.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (11) : 4084 - 4089
[10] TOWARDS AN ACCURATE ABINITIO CALCULATION OF THE TRANSITION-STATE STRUCTURES OF THE DIELS-ALDER REACTION
BERNARDI, F
BOTTONI, A
ROBB, MA
FIELD, MJ
HILLIER, IH
GUEST, MF
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (15) : 1051 - 1052

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