We are grateful to the National Science Foundation for financial support and NCSA (TG-CHE040005N) for computer time. Trajectory animations of reactions of 1,3-dipoles with acetylene and ethylene are available online at http://www.chem.ucla.edu/∼lxu01pku.
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Communication
Dynamics of 1,3-Dipolar Cycloaddition Reactions of Diazonium Betaines to Acetylene and Ethylene: Bending Vibrations Facilitate Reaction†
Article first published online: 20 FEB 2009
DOI: 10.1002/anie.200805906
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Xu, L., Doubleday, Charles E. and Houk, K. N. (2009), Dynamics of 1,3-Dipolar Cycloaddition Reactions of Diazonium Betaines to Acetylene and Ethylene: Bending Vibrations Facilitate Reaction. Angew. Chem. Int. Ed., 48: 2746–2748. doi: 10.1002/anie.200805906
- †
Publication History
- Issue published online: 24 MAR 2009
- Article first published online: 20 FEB 2009
- Manuscript Received: 4 DEC 2008
Funded by
- National Science Foundation
- TG-CHE040005N
Keywords:
- cycloaddition;
- cyclo-diradicals;
- dipole bending;
- trajectory calculations;
- transition states
Abstract
Getting the bends: The dynamics of 1,3-dipolar cycloaddition reactions have been explored by decomposing transition vector, quasi-classical trajectories, and single trajectories. Dipole bending (see picture) makes the largest contribution to the TS distortion energy and constitutes the major part of transition-state distortion energy in the favored concerted pathway.