18684-82-7Relevant articles and documents
Synthesis of 3-Substituted Indolizines from the Reaction of Chlorocarbenes with 2-Vinylpyridine
Bonneau, Roland,Romashin, Yuri N.,Liu, Michael T. H.,MacPherson, Spenser E.
, p. 509 - 510 (1994)
3-Substituted indolizines have been obtained in a one-step procedure from the reaction of chlorocarbenes with 2-vinylpyridine.
Catalytic olefination. Estimation of the reactivity of polyhaloalkanes
Nenaidenko,Korotchenko,Shastin,Tyurin,Balenkova
, p. 1750 - 1756 (2007/10/03)
Global electrophilicity indices and carbon-halogen bond energies of a wide series of halogen derivatives were calculated in terms of the density functional theory (DFT). The calculated values were used to estimate the reactivity of halogen derivatives under conditions of catalytic olefination. Reactions of N-unsubstituted hydrazones with polyhaloalkanes in the presence of CuCl afforded substituted alkenes. The relation between the structure of polyhaloalkanes and their reactivity was studied using the reaction with 4-chlorobenzaldehyde hydrazone as an example. It was found that increase in the global electrophilicity index and decrease in the C-Hlg bond energy are accompanied by increase in the olefinating power of halogen derivatives.
Catalytic olefination reaction of carbonyl compounds. A study on stereoselectivity of alkene formation
Nenaidenko,Korotchenko,Shast,Tyur,Balenkova
, p. 1835 - 1840 (2007/10/03)
The mechanism of formation of alkene stereoisomers in the catalytic olefination reaction of carbonyl compounds was studied. 4-Chlorobenzaldehyde hydrazone 1 stereoselectively reacts with a number of F-, Cl-, Br-, and I-containing polyhaloalkanes in the presence of catalytic amounts of CuCl to give ω-substituted styrenes 2 with the more thermodynamically stable alkene isomer being the major product. A model for the formation of the stereoisomers of alkenes 2 in the olefination reaction is proposed. Stereoselectivity of the reaction is determined by elimination of copper(II) halides from the lowest-lying conformers of organocopper intermediates II. According to quantum-chemical calculations, the elimination should involve the staggered conformations with antiperiplanar arrangement of C-Hal and C-Cu bonds and proceed by the E2 anti-elimination mechanism. The results of quantum-chemical calculations are in good agreement with the experimental E/Z alkene isomer ratios.
