6707-86-4Relevant academic research and scientific papers
Convenient preparative synthesis of pentacyclo[5.3.0.02,5.03,9.04,8]decane (C 2-Bishomocubane)
Sklyarova,Rodionov,Fokin
experimental part, p. 1633 - 1636 (2010/05/03)
By reaction of pentacyclo[5.3.0.02,5.03,9.04,8]decane-6,10-dione 6-ethyleneketal with lithium aluminum hydride the corresponding hydroxyketal was obtained whose hydroxy group was replaced by chlorine at boiling in CCl4 in the presence of a 15% molar excess of triphenylphosphine. 6-Ethyleneketal of pentacyclo-[5.3.0.02,5.03,9.04,8]decan-6-one obtained by dechlorination of the chloroketal in a system lithium-t-BuOH in THF was hydrolyzed to ketone by heating in 10% sulfuric acid in the presence of THF. The obtained ketone was reduced along Wolf-Kishner reaction to pentacyclo[5.3.0.02,5.03,9.04,8]decane.
Light-promoted catalytic hydrogenation of olefins with nickel complexes: the formation of nickel hydrides from the reaction of Ni(I) complexes with hydrogen
Chow, Yuan L.,Li, Huali,Yang, Meng-Su
, p. 2920 - 2927 (2007/10/02)
The conditions pertaining to triplet excited state ketone-sensitized photoreduction of Ni(acac)2 under hydrogen were show to serve as a method for light-promoted hydrogenation of olefins with clean chemospecificity.For example, the double bond in the bicyclic system was preferentially hydrogenated over the other double bond in dicyclopentediene and in 5-methylenebicycloheptene.This photohydrogenation could be run under a wide range of conditions and was apparently a homogeneous catalytic process; in a late stage of photohydrogenation, concurrence of heterogeneous catalytic processes was not ruled out.The Ni(I) complexes of tetrahydrofuran and olefins generated from the photoreduction of Ni(acac)2 were shown to react with hydrogen to give nickel hydride complexes.By analogy with the generally accepted reaction pattern, coordinated olefins in these nickel hydride complexes probably spontaneously undergo intramolecular addition to give Ni-alkyl complexes.It is suggested, that these Ni-alkyl complexes are photoexcited to generate a vacant coordination site so that the reaction with hydrogen can proceed to give products and regenerate a nickel hydride catalyst.
Triplet States of Cyclic Olefins and Dienes. On the Lifetimes and Chemical Reactivities Studied by Pulse Radiolysis
Nakabayashi, Kenichi,Toki, Susumu,Takamuku, Setsuo
, p. 1889 - 1892 (2007/10/02)
Triplet lifetimes of cyclic olefins and dienes measured by pulse radiolysis are dependent on the ring size which affects the most stable conformation of the triplet.In the case of cyclic nonconjugated dienes, an intramolecular biradical formation is an important decay process when the reaction is sterically allowed.
SYNTHESIS AND -CYCLOREVERSION OF CAGE KETONES
Yamashita, Yoshiro,Mukai, Toshio
, p. 1741 - 1744 (2007/10/02)
A series of pentacyclic cage ketones 2b-d having no substituent was synthesized by the photochemical -cycloaddition reaction of corresponding tricyclic dienones 1b-d.The cage ketones 2b-d underwent thermal -cycloreversion to give dienones 1b-d.The reactivities were dependent on the length of the bridge "X".
Carbonylation and Valence Isomerization of 1,3-Dihomocubane Derivatives by Chlorodicarbonylrhodium Dimer
Zlotogorski, Changa,Blum, Jochanan,Osawa, Eiji,Schwartz, Helmut,Hoehne, Gerhard
, p. 971 - 976 (2007/10/02)
1,3-Dihomocubane and several analogous cage compounds react with Rh2(CO)4Cl2 to give dinuclear acyl-rhodium complexes.These complexes are transformed into dicyclopentadiene and/or D3-trihomocubanone derivatives either upon heating or by treatment with triphenylphosphine. 1,3-Ethanomethanocubane reacts analogously.The kinetics of these metal-induced transformations follow the second-order rate law.A linear relationship exists between the constants and the calculated strain energies of the starting cage compounds.
