627-58-7Relevant articles and documents
Selective enzymatic epoxidation of dienes: Generation of functional enantiomerically enriched diene monoepoxy monomers
Hu, Shanghui,Gupta, Pankaj,Prasad, Ashok K,Gross, Richard A,Parmar, Virinder S
, p. 6763 - 6766 (2002)
Enantiomerically enriched diene monoepoxides were selectively synthesized using oxidases from Pseudomonas sp. and chloroperoxidase from Caldariomyces fumago. These monoepoxides are useful monomers for generating functional chiral polymeric materials.
Kinetics and Mechanism of Thermal Decomposition of Bis(Η3-Allyl)Nickel Complexes
Flid,Zamalyutin,Shamsiev,Katsman
, p. 113 - 117 (2019/05/27)
Abstract: The kinetics of thermal decomposition of bis(η3-allyl) nickel complexes in various media is studied. The specific features of the mechanism are determined, including the combination of the stages of trans-cis isomerization of Niall2 and the bimolecular decomposition of the cis-isomer with diallyl formation. The effect of autocatalytic decomposition of complexes with metallic nickel is been detected. The qualitative dependences of the process rate on the nature of the solvent and the structure of the allyl ligand are determined. The activation parameters of individual steps, consistent with quantum chemical calculations, are found.
Gold(I)-catalyzed intermolecular [2+2] cycloaddition of alkynes with alkenes
Lopez-Carrillo, Veronica,Echavarren, Antonio M.
supporting information; experimental part, p. 9292 - 9294 (2010/11/03)
The gold(I)-catalyzed intermolecular reaction of terminal alkynes with alkenes leads to cyclobutenes. The use of sterically hindered cationic Au(I) complexes as catalysts is key for the success of this reaction.
Mechanism of the diphenyldisulfone-catalyzed isomerization of alkenes. Origin of the chemoselectivity: Experimental and quantum chemistry studies
Markovic, Dean,Varela-Alvarez, Adrian,Sordo, Jose Angel,Vogel, Pierre
, p. 7782 - 7795 (2007/10/03)
Polysulfone- and diphenyldisulfone-catalyzed alkene isomerizations are much faster for 2-alkyl-1-alkenes than for linear, terminal alkenes. The mechanism of these reactions has been investigated experimentally for the isomerization of methylidenecyclopentane into 1-methylcyclopentene, and theoretically [CCSD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) calculations] for the reactions of propene and 2-methylpropene with a methanesulfonyl radical, MeSO 2?. On heating, polysulfones and (PhSO2)2 equilibrate with sulfonyl radicals, RSO2?. The latter abstract allylic hydrogen atoms in one-step processes giving allylic radical/RSO 2H pairs that recombine within the solvent cage producing the corresponding isomerized alkene and RSO2?. The sulfinic acid, RSO2H, can diffuse out from the solvent cage (H/D exchange with MeOD,D2O) and reduce an allyl radical. Calculations did not support other possible mechanisms such as hydrogen exchange between alkenes, electron transfer, or addition/elimination process. Kinetic deuterium isotopic effects measured for the (PhSO2)2-catalyzed isomerization of methylidenecyclopentane and deuterated analogues and calculated for the H abstraction from 2-methylpropene and deuterated analogues by CH 3-SO2? are consistent also with the one-step hydrogen transfer mechanism. The high chemoselectivity for this reaction is not governed by an exothermicity difference but by a difference in ionization energies of the alkenes. Calculations for CH3SO2? + propene and CH3SO2? + 2-methylpropene show a charge transfer of 0.34 and 0.38 electron, respectively, from the alkenes to the sulfonyl radical in the transition states of these hydrogen abstractions.
