695-90-9Relevant articles and documents
Cleavage vs Rearrangement Ratios and Secondary Deuterium Kinetic Isotope Effects in the Thermolysis of Conformationally Fixed Cisoid Vinylcyclobutanes
Gajewski, Joseph J.,Paul, Gitendra
, p. 1986 - 1989 (2007/10/02)
The first-order rate constants for the thermally induced retro 2+2 cleavage and rearrangement of 5-methylenespirononane occur in a 1:2 ratio.In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes.Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted.For the rearrangement of 5-methylenespirooctane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (kH/kD2) is 1.086 +/- 0.023.This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate.The secondary KIE for cleavage of 5-methylenespirooctane is 1.025 +/- 0.027.
The Disproportionation of cis-Bicyclonona-3,7-diene Catalyzed by Fe(CO)5 and Cp2Fe2(CO)4
Kagayama, Takashi,Okabayashi, Shinji,Amaike, Yoichi,Matsukawa, Yasuo,Ishii, Yasutaka,Ogawa, Masaya
, p. 2297 - 2298 (2007/10/02)
cis-Bicyclonona-3,7-diene (1) was catalytically disproportionated by the use of Fe(CO)5 and Cp2Fe2(CO)4 to bicyclonon-1(6)-ene (3) and indan (4).However, the same reaction catalyzed by the use of other metal carbonyls gave merely small amount of 3 and 4, while those using Pd- and Rh-carbons yielded only 4 and the starting material, 1, respectively.