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

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-...

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Autores principales: Leber, Phyllis A., Nocket, Anthony J., Hancock-Cerutti, William, Bemis, Christopher Y., Khine, Wint Khant, Mohrbacher III, Joseph A., Baldwin, John E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2014
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6271342/
https://www.ncbi.nlm.nih.gov/pubmed/24473211
http://dx.doi.org/10.3390/molecules19021527
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author Leber, Phyllis A.
Nocket, Anthony J.
Hancock-Cerutti, William
Bemis, Christopher Y.
Khine, Wint Khant
Mohrbacher III, Joseph A.
Baldwin, John E.
author_facet Leber, Phyllis A.
Nocket, Anthony J.
Hancock-Cerutti, William
Bemis, Christopher Y.
Khine, Wint Khant
Mohrbacher III, Joseph A.
Baldwin, John E.
author_sort Leber, Phyllis A.
collection PubMed
description 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: k(ep) > k(13 ) > k(f) > k(CPC).
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spelling pubmed-62713422018-12-20 Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo) Leber, Phyllis A. Nocket, Anthony J. Hancock-Cerutti, William Bemis, Christopher Y. Khine, Wint Khant Mohrbacher III, Joseph A. Baldwin, John E. Molecules Article 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: k(ep) > k(13 ) > k(f) > k(CPC). MDPI 2014-01-27 /pmc/articles/PMC6271342/ /pubmed/24473211 http://dx.doi.org/10.3390/molecules19021527 Text en © 2014 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
spellingShingle Article
Leber, Phyllis A.
Nocket, Anthony J.
Hancock-Cerutti, William
Bemis, Christopher Y.
Khine, Wint Khant
Mohrbacher III, Joseph A.
Baldwin, John E.
Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title_full Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title_fullStr Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title_full_unstemmed Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title_short Gas Phase Thermal Reactions of exo-8-Cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
title_sort gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo)
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6271342/
https://www.ncbi.nlm.nih.gov/pubmed/24473211
http://dx.doi.org/10.3390/molecules19021527
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