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Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).

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 ?-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.

SUBMITTER: Leber PA

PROVIDER: S-EPMC6271342 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Gas phase thermal reactions of exo-8-cyclopropyl-bicyclo[4.2.0]oct-2-ene (1-exo).

Leber Phyllis A PA Nocket Anthony J AJ Hancock-Cerutti William W Bemis Christopher Y CY Khine Wint Khant WK Mohrbacher Iii Joseph A JA Baldwin John E JE

Molecules (Basel, Switzerland) 20140127 2

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 vinylcyclopropa ...[more]

PMID: 24473211

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