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Molecules 2014, 19(2), 1527-1543; doi:10.3390/molecules19021527
Article

Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)

1,* , 1
, 1
, 1
, 1
, 1
 and 2
1 Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA 2 Department of Chemistry, Syracuse University, Syracuse, NY 13244-4100, USA
* Author to whom correspondence should be addressed.
Received: 19 December 2013 / Revised: 10 January 2014 / Accepted: 15 January 2014 / Published: 27 January 2014
(This article belongs to the Special Issue Gas Phase Reactions)
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Abstract

The title compound 1-exo (with minor amounts of its C8 epimer 1-endo) was prepared by Wolff-Kishner reduction of the cycloadduct of 1,3-cyclohexadiene and cyclopropylketene. The [1,3]-migration product 2-endo was synthesized by efficient selective cyclopropanation of endo-5-vinylbicyclo[2.2.2]oct-2-ene at the exocyclic π-bond. Gas phase thermal reactions of 1-exo afforded C8 epimerization to 1-endo, [1,3]- migrations to 2-exo and 2-endo, direct fragmentation to cyclohexadiene and vinylcyclopropane, and CPC rearrangement in the following relative kinetic order: kep > k13 > kf > kCPC.
Keywords: gas phase reaction; thermal chemistry; [1,3]-sigmatropic rearrangement; [1,3]-carbon migration; CPC rearrangement gas phase reaction; thermal chemistry; [1,3]-sigmatropic rearrangement; [1,3]-carbon migration; CPC rearrangement
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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MDPI and ACS Style

Leber, P.A.; Nocket, A.J.; Hancock-Cerutti, W.; Bemis, C.Y.; Khine, W.K.; Mohrbacher III, J.A.; Baldwin, J.E. Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo). Molecules 2014, 19, 1527-1543.

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