78370-38-4Relevant academic research and scientific papers
Cyclization of 1,6-enynes catalyzed by gold nanoparticles supported on TiO2: Significant changes in selectivity and mechanism, as compared to homogeneous Au-catalysis
Gryparis, Charis,Efe, Christina,Raptis, Christos,Lykakis, Ioannis N.,Stratakis, Manolis
supporting information; experimental part, p. 2956 - 2959 (2012/08/07)
Gold nanoparticles supported on TiO2 (1.2 mol %) catalyze, for the first time under heterogeneous conditions, the cycloisomerization of a series of 1,6-enynes in high yields. In several cases, the product selectivity differs significantly as compared to homogeneous Au(I)-catalysis. Based on product analysis and stereoisotopic studies it is proposed that the major or exclusive pathway involves a 5-exo cyclization mode to form stereoselectively gold cyclopropyl carbenes that undergo a single cleavage pathway, in contrast to homogeneous Au-catalysis where the double cleavage pathway operates substantially.
Asymmetric catalysis. Mechanism of asymmetric catalytic intramolecular hydrosilation
Bergens, Steven H.,Noheda, Pedro,Whelan, John,Bosnich
, p. 2128 - 2135 (2007/10/02)
The mechanism of asymmetric catalytic intramolecular hydrosilation using [Rh(diphosphine)]+ catalysts has been investigated by the use of specifically labeled deuterated substrates. It is concluded that oxidative addition of the silicon hydride
2H>Allyl Radical: Barrier to Rotation and Allyl Delocalization Energy
Korth, Hans-Gert,Trill, Heinrich,Sustmann, Reiner
, p. 4483 - 4489 (2007/10/02)
Syn and anti 2H>allyl radicals are generated from deuterated allyl phosphites by attack of tert-butoxy radicals, and their interconversion is studied in the temperature range of 50-100 deg C.Steady-state kinetic analysis together with time-resolved measurements of the diffusion-controlled recombination kinetics yield an allyl rotational barrier of 15.7 +/- 1.0 kcal/mol (logA = 13.5 +/- 0.5).From this a value of 14.0-14.5 kcal/mol is deduced for the allyl delocalization energy.
