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

Molecules

Phyllis A. Leber¹  Anthony J. Nocket¹  William Hancock-Cerutti¹  Christopher Y. Bemis¹  Wint Khant Khine¹  Joseph A. Mohrbacher III¹ 

[1] Department of Chemistry, Franklin & Marshall College, Lancaster, PA 17604-3003, USA; E-Mails:

关键词: gas phase reaction;    thermal chemistry;    [1;    3]-sigmatropic rearrangement;    [1;    3]-carbon migration;    CPC rearrangement;   

DOI  :  10.3390/molecules19021527

来源: mdpi

【 摘 要 】

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 > k₁₃ > k_f > k_CPC.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.