Strained hydrocarbons from cyclic diynes

• Verfasst von: Bethke, Sabine [VerfasserIn]
• Verfasst von: Brand, Stefan [VerfasserIn]
• Verfasst von: Treptow, Björn [VerfasserIn]
• Verfasst von: Gleiter, Rolf [VerfasserIn]
• Titel: Strained hydrocarbons from cyclic diynes
• Titelzusatz: preparation and reactivity
• Verf.angabe: Sabine Bethke, Stefan Brand, Björn Treptow and Rolf Gleiter
• E-Jahr: 2002
• Jahr: 28 June 2002
• Umfang: 6 S.
• Fussnoten: Gesehen am 04.11.2020
• Titel Quelle: Enthalten in: Journal of physical organic chemistry
• Ort Quelle: Chichester : Wiley, 1988
• Jahr Quelle: 2002
• Band/Heft Quelle: 15(2002), 8, Seite 484-489
• ISSN Quelle: 1099-1395
• DOI: doi:10.1002/poc.500
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: alkynes
• Sach-SW: cage compounds
• Sach-SW: DFT calculations
• Sach-SW: photochemistry
• Sach-SW: strained hydrocarbons
• Sach-SW: thermal rearrangements
• K10plus-PPN: 1737730065

Abstract

The reaction of cyclic diynes with either CpCo(CO)2 or AlCl3 yielded strained hydrocarbons in which a Dewar benzene or a tricyclo[4.2.0.02,5]octa-3,7-diene frame is bridged by hydrocarbon chains. The photochemistry and thermochemistry of these species are discussed. Results of quantum chemical calculations (DFT, CASPT2) are used to discuss the thermochemistry of four different fourfold bridged tricyclo[4.2.0.02,5]octa-3,7-dienes. Depending on the bridging mode, either a Cope-type rearrangement or a ring opening reaction is preferred. Copyright © 2002 John Wiley & Sons, Ltd.