Lalitha, S. ; Chandrasekhar, Jayaraman ; Mehta, Goverdhan (1990) Acceleration of cope rearrangement by a remote carbenium ion center: theoretical elucidation of the electronic origin Journal of Organic Chemistry, 55 (11). pp. 3455-3457. ISSN 0022-3263
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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo00298a015
Related URL: http://dx.doi.org/10.1021/jo00298a015
Abstract
The electronic origin of the remarkable acid catalysis of Cope rearrangement found recently in a rigid tetracyclic framework, I, has been probed by means of MNDO calcns. on model systems II and III. The Cope rearrangement paths are calcd. to be fundamentally different for the neutral and the cationic systems. A step-wise process involving two intermediates is the min. energy reaction pathway (MERP) for the Cope rearrangement of the cation III. The calcns. also reveal another intriguing possibility involving a remarkable pyramidal carbocation intermediate IV which is essentially a diolefin π-complex of CH+. Both these paths require substantially less activation enthalpies than that computed for the rearrangement of the neutral mol. II.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 7279 |
Deposited On: | 25 Oct 2010 11:57 |
Last Modified: | 05 Feb 2011 08:30 |
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