Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels–Alder reactions
作者： Diana Yepes , Jane S Murray , Patricia Pérez , Luis R Domingo , Peter Politzer
DOI: 10.1039/C3CP54766C
关键词:
摘要: We have computationally compared three Diels-Alder cycloadditions involving cyclopentadiene and substituted ethylenes; one of the reactions is synchronous, while others are slightly or highly asynchronous. Synchronicity weak asynchronicity characterized by reaction force constant κ(ξ) having just a single minimum in transition region along intrinsic coordinate ξ, for high has negative maximum with minima on both sides. The electron localization function (ELF) shows that features can be directly related to formation new C-C bonds between diene dienophile. There thus striking complementarity ELF; identifies key points ξ ELF describes what happening at those points.
rsc.org
harvard.edu
unab.cl
sci-hub.se 参考文章(55)
Peter Politzer, Alejandro Toro-Labbé, Soledad Gutiérrez-Oliva, Jane S. Murray, Perspectives on the Reaction Force Advances in Quantum Chemistry Volume 64. ,vol. 64, pp. 189- 209 ,(2012) , 10.1016/B978-0-12-396498-4.00006-5
W. Carruthers, Cycloaddition reactions in organic synthesis ,(1990)
Jaroslav V. Burda, Jane S. Murray, Alejandro Toro-Labbé, Soledad Gutiérrez-Oliva, Peter Politzer, Reaction force analysis of solvent effects in the addition of HCl to propene. Journal of Physical Chemistry A. ,vol. 113, pp. 6500- 6503 ,(2009) , 10.1021/JP9025927
John C. Polanyi, Ahmed H. Zewail, Direct Observation of the Transition State Accounts of Chemical Research. ,vol. 28, pp. 119- 132 ,(1995) , 10.1021/AR00051A005
K. Black, P. Liu, L. Xu, C. Doubleday, K. N. Houk, Dynamics, transition states, and timing of bond formation in Diels–Alder reactions Proceedings of the National Academy of Sciences of the United States of America. ,vol. 109, pp. 12860- 12865 ,(2012) , 10.1073/PNAS.1209316109
Henri B. Kagan, Olivier Riant, Catalytic Asymmetric Diels-Alder Reactions Chemical Reviews. ,vol. 92, pp. 1007- 1019 ,(1992) , 10.1021/CR00013A013
Daniel H. Ess, K. N. Houk, Theory of 1,3-Dipolar Cycloadditions: Distortion/Interaction and Frontier Molecular Orbital Models Journal of the American Chemical Society. ,vol. 130, pp. 10187- 10198 ,(2008) , 10.1021/JA800009Z
M. G. Evans, M. Polanyi, Inertia and driving force of chemical reactions Transactions of The Faraday Society. ,vol. 34, pp. 11- 24 ,(1938) , 10.1039/TF9383400011
Jane S. Murray, Peter Politzer, The electrostatic potential: an overview Wiley Interdisciplinary Reviews: Computational Molecular Science. ,vol. 1, pp. 153- 163 ,(2011) , 10.1002/WCMS.19
Lai Xu, Charles E. Doubleday, K. N. Houk, Dynamics of 1,3-dipolar cycloadditions: energy partitioning of reactants and quantitation of synchronicity. Journal of the American Chemical Society. ,vol. 132, pp. 3029- 3037 ,(2010) , 10.1021/JA909372F