37745-07-6Relevant academic research and scientific papers
CATALYTIC CONVERSIONS OF CYCLIC C3-OLEFINS IN THE PRESENCE OF METAL COMPLEXES. 6. EFFECT OF P(NEt2)3 LIGAND ON THE PROPERTIES OF COMPLEX Ni(0) CATALYST IN OLIGOMERIZATION OF METHYLENECYCLOPROPANE
Furman, D. B.,Munshieva, M. K.,Ivanov, A. O.,Belyankin, A. Yu.,Morozova, L. N.,et al.
, p. 465 - 469 (2007/10/02)
Preferential formation of di- or trimers of methylenecyclopropane (MCP) under influence of Ni(0) complexes is determined by the nature of ligands, additions of modifiers, and the reaction conditions.The Ni(0) complex with coordinated P(NEt2)3 was synthesized via a proposed intermediate catalytic system (Ni(COD)2-P(NEt2)3 by the interaction between Ni(η3-C3H5)2 and P(NEt2)3.The composition of the complex: 2>x (K-1) was established by 1H and 31P- NMR, EPR spectroscopy, IR diffuse reflectance spectroscopy, and GLC.In the range 20-60 deg C complex K-1 only brings about trimerization of MCP.The catalytic properties of K-1 were described earlier by a proposed scheme for the catalytic conversion of MCP under the influence of Ni(0) complexes.
Metallacycloalkanes, VI. Five- to Seven-membered (2,2'-Bipyridine)nickelacycloalkanes from Methylenecyclopropane and Nickel(0) Compounds
Binger, Paul,Doyle, Michael J.,Benn, Reinhard
, p. 1 - 10 (2007/10/02)
Depending on the reaction conditions (2,2'-bipyridine)(η2-methylenecyclopropane)nickel (4) or the (2,2'-bipyridine)nickelacycloalkanes 5 - 8 were obtained from methylenecyclopropane (1) and (2,2'-bipyridine)(1,5-cyclooctadiene)nickel.The complexes were characterized spectroscopically and by decomposition reactions. 5 - 8 react with methyl acrylate under reductive elimination to give the cycloalkanes 2 (from 5), 3 (from 6a, b), or 9 (from 7).With CO 5 reacts additionally through an insertion to yield the cyclopentanone derivative 10.Alcoholysis of 5 with ethanol affords 2-cyclopropylmethyl-1-butene (11), whereas with phenol the new (2,2'-bipyridine)nickel complex 12 was formed.
Reactions of Methylenecyclopropanes, VII. Nickel(0)-catalysed Cycloadditions of Methylenecyclopropanes with Alkyl Acrylates
Binger, Paul,Brinkmann, Axel,Wedemann,Petra
, p. 2920 - 2930 (2007/10/02)
Cycloaddition reactions of methylenecyclopropane (1) and of the ring-methylated methylenecyclopropanes 5, 9, and 12 with alkyl acrylates are performed at nickel(0) catalysts, such as bis(1,5-cyclooctadiene)nickel under mild conditions (0 - 50 deg C).Depending on the degree of methylation of the three-membered ring, 1 and 5 give only alkyl 3-methylenecyclopentanecarboxylates (4 and 6), whereas 9 leads to a mixture of the methylenecyclopentane derivative 10 and the alkyl spirohexanecarboxylate 11, and 12 react to form only the spirohexane derivative 13.With 12 isomerisation to 2,3,3-trimethyl-1,4-pentadiene (15) also takes place.In the case of 9 the ratio of methylenecyclopentane to spirohexanecarboxylate can be influenced by the size of alkyl groups. - In the Ni0-catalysed reactions of 1 with substituted acrylates (methyl crotonate or diethyl maleate) codimerisation to 16 and 17 competes with cyclodimerisation to 2 and 3.
Reactions of Methylenecyclopropanes, V. Palladium(0)-catalyzed Codimerisation of Methylenecylopropane with Methyl Acrylates and 1,2-Ethylenedicarbonic Esters
Binger, Paul,Schuchardt, Ulf
, p. 3313 - 3324 (2007/10/02)
Triorganylphosphane-modified palladium(0) compounds catalyze the codimerisation of methylenecyclopropane (1) with methyl acrylate, methyl trans-crotonate or trans-cinnamate to give the methylenecyclopentanecarboxylic esters 3, 4, 5; diethyl fumarate or dimethyl maleate and 1 lead to the methylenecyclopentanedicarbonic esters 12.With diethyl maleate besides cis/trans-12b also oligomers containing two mols of 1 and one (cis/trans-14) or two mols of the diester (cis/trans-15) are formed.
Reactions of Methylenecyclopropane, IV. Palladium(0)-catalyzed Codimerization of Methylenecyclopropane with Alkenes
Binger, Paul,Schuchardt, Ulf
, p. 3334 - 3341 (2007/10/02)
Triorganylphosphane-modified palladium(0) compounds catalyze the codimerization of methylenecyclopropane (1) with ethylene, norbornene, dicyclopentadiene or norbornadiene to give substituted methylenecyclopentane derivatives 3-7.In all of these reactions the three-membered ring of 1 is opened between C2 and C3. 1-Alkenes, alkenes with an internal double bond and unstrained cycloalkenes as well as alkynes and 1,3-butadiene do not react in this manner.
Reactions of Methylenecyclopropane, III. Cooligomerization of Methylenecyclopropane with Allenes on Palladium(0) Catalysts
Binger, Paul,Schuchardt, Ulf
, p. 1063 - 1071 (2007/10/02)
The cooligomerization of methylenecyclopropane (1) with allene, 1,1-dimethylallene or 1,2-cyclononadiene on a palladium(0) catalyst has been investigated.Exclusive formation of cyclic products, viz 1,3-dimethylenecyclopentane (3) and 1,3,5-trimethylenecyc
