Dynamic control of dichlorocarbene addition to cyclopropene
作者： Dina C. Merrer , Charles Doubleday
DOI: 10.1002/POC.1883
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摘要: The addition of dichlorocarbene to cyclopropene has been studied with direct dynamics quasiclassical trajectories using B3LYP/6-31G*. yielded 1,1-dichlorobicyclo[1.1.0]butane and 1,1-dichloro-1,3-butadiene in a ratio 4.7:1, which is consistent the experimental 4:1. large majority formed products within 100 fs start trajectory proceeded concerted manner bicyclobutane or butadiene; no zwitterion biradical intermediate was observed. Eight generated subsequently dissociated chloride form an ion pair, recombined 2,3-dichlorocyclobutene. lifetime pair averaged 95 fs, too short be considered intermediate, previous calculations that characterized as transition state. This study lends strong support proposition CCl2 controlled by dynamic effects. Copyright © 2011 John Wiley & Sons, Ltd.
sci-hub.se 参考文章(36)
Gilles H. Peslherbe, Haobin Wang, William L. Hase, Monte Carlo Sampling for Classical Trajectory Simulations Advances in Chemical Physics. ,vol. 105, pp. 171- 201 ,(2007) , 10.1002/9780470141649.CH6
Charles Doubleday, Mechanism of the Vinylcyclopropane−Cyclopentene Rearrangement Studied by Quasiclassical Direct Dynamics Journal of Physical Chemistry A. ,vol. 105, pp. 6333- 6341 ,(2001) , 10.1021/JP010464Z
Vebjørn Bakken, David Danovich, Sason Shaik, H. Bernhard Schlegel, A Single Transition State Serves Two Mechanisms: An ab Initio Classical Trajectory Study of the Electron Transfer and Substitution Mechanisms in Reactions of Ketyl Radical Anions with Alkyl Halides Journal of the American Chemical Society. ,vol. 123, pp. 130- 134 ,(2001) , 10.1021/JA002799K
Daniel A. Singleton, Chao Hang, Michael J. Szymanski, Matthew P. Meyer, Andrew G. Leach, Keith T. Kuwata, Jenny S. Chen, Alexander Greer, Christopher S. Foote, K. N. Houk, Mechanism of Ene Reactions of Singlet Oxygen. A Two-Step No-Intermediate Mechanism Journal of the American Chemical Society. ,vol. 125, pp. 1319- 1328 ,(2003) , 10.1021/JA027225P
Hiroshi Yamataka, Misako Aida, Michel Dupuis, One transition state leading to two product states: ab initio molecular dynamics simulations of the reaction of formaldehyde radical anion and methyl chloride Chemical Physics Letters. ,vol. 300, pp. 583- 587 ,(1999) , 10.1016/S0009-2614(98)01440-7
Tefsit Bekele, Chad F. Christian, Mark A. Lipton, Daniel A. Singleton, "Concerted" transition state, stepwise mechanism. Dynamics effects in C2-C6 enyne allene cyclizations. Journal of the American Chemical Society. ,vol. 127, pp. 9216- 9223 ,(2005) , 10.1021/JA0508673
Charles Doubleday, Maja Nendel, K. N. Houk, David Thweatt, Michael Page, Direct Dynamics Quasiclassical Trajectory Study of the Stereochemistry of the Vinylcyclopropane−Cyclopentene Rearrangement Journal of the American Chemical Society. ,vol. 121, pp. 4720- 4721 ,(1999) , 10.1021/JA984083J
Nihan Çelebi-Ölçüm, Daniel H. Ess, Viktorya Aviyente, K. N. Houk, Effect of Lewis acid catalysts on Diels-Alder and hetero-Diels-Alder cycloadditions sharing a common transition state. Journal of Organic Chemistry. ,vol. 73, pp. 7472- 7480 ,(2008) , 10.1021/JO801076T
Aviva E. Litovitz, Ivan Keresztes, Barry K. Carpenter, Evidence for nonstatistical dynamics in the Wolff rearrangement of a carbene. Journal of the American Chemical Society. ,vol. 130, pp. 12085- 12094 ,(2008) , 10.1021/JA803230A
Charles Doubleday, Kim Bolton, William L. Hase, Direct Dynamics Study of the Stereomutation of Cyclopropane Journal of the American Chemical Society. ,vol. 119, pp. 5251- 5252 ,(1997) , 10.1021/JA964250K