Cope Reaction Families: To Be or Not to Be a Biradical
- 22 July 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 6 (17) , 2981-2984
- https://doi.org/10.1021/ol0488340
Abstract
The cyclization reactions of polyunsaturated systems such as enediynes, enyne-allenes, as well as many others, can be structurally related to the Cope reaction and grouped into two branches: 6π (e.g., Cope, allenyl-Cope) and [2σ + 4π] systems (e.g., Bergman, Myers−Saito). After extensive computional (BCCD(T)/cc-pVDZ//UBLYP/6-31G*) examination of a large set of Cope-related reactions, we derive the following simple rule: biradical intermediates are involved along the reaction path if they are stabilized by allylic resonance or aromaticity.This publication has 19 references indexed in Scilit:
- Implicit and Explicit Coverage of Multi-reference Effects by Density Functional TheoryInternational Journal of Molecular Sciences, 2002
- Can Fulvenes Form from Enediynes? A Systematic High-Level Computational Study on Parent and Benzannelated Enediyne and Enyne−Allene CyclizationsThe Journal of Physical Chemistry A, 2001
- Cooperative and Competitive Substituent Effects on the Cope Rearrangements of Phenyl-Substituted 1,5-Hexadienes Elucidated by Becke3LYP/6-31G* CalculationsJournal of the American Chemical Society, 2000
- Bergman, Aza-Bergman, and Protonated Aza-Bergman Cyclizations and Intermediate 2,5-Arynes: Chemistry and Challenges to ComputationJournal of the American Chemical Society, 1998
- The Importance of Including Dynamic Electron Correlation in ab Initio CalculationsAccounts of Chemical Research, 1996
- Stereochemical dissection of a carbene fragmentation reactionJournal of the American Chemical Society, 1992
- Concave functionality: intracavity phosphine oxide as a locus of complexationJournal of the American Chemical Society, 1989
- The role of d functions in sulfur oxide moleculesJournal of the American Chemical Society, 1989
- Density-functional exchange-energy approximation with correct asymptotic behaviorPhysical Review A, 1988
- Structure and reactivity of organic ions in gas-phase radiolysis. V. Structure and formation process of the C7H7+ ion from tolueneJournal of the American Chemical Society, 1972