19901-79-2Relevant academic research and scientific papers
Selective Catalytic Hydrogenation of Alicyclic Dienes with Hydrogen in a Liquid Phase
Bermeshev,Antonova,Shangareev,Danilova,Pozharskaya
, p. 869 - 875 (2018)
Abstract: The hydrogenation behavior of a number of alicyclic dienes (5-vinyl-2-norbornene (5-vinyl-bicyclo[2.2.1]heptene-2), dicyclopentadiene (tricyclo[5.2.1.02,6]decadiene-3,8), and cis,cis-1,5-cyclooctadiene) to the corresponding cycloalkenes in the presence of a finely divided palladium catalyst suspended in the liquid phase has been studied. The reactivities of the double bonds of these dienes have been compared. The conversion of 5-vinyl-2-norbornene and selectivity of its hydrogenation to 2-vinylnorbornane depending on the reaction conditions have been evaluated. Conditions for the selective production of desired 2-vinylnorbornane are proposed for the further implementation of this process in practice.
SOME NOVELTIES IN OLEFIN CARBOMETALLATION ASSISTED BY ALKYL-MAGNESIUM AND -ALUMINIUM DERIVATIVES AND CATALYZED BY ZIRCONIUM AND TITANIUM COMPLEXES
Dzhemilev, U. M.,Vostrikova, O. S.
, p. 43 - 52 (1985)
Carbometallation of α-olefins, as well as of those containing functional groups, and of norbornene derivatives has been investigated with alkyl-magnesium and -aluminium compounds and found to proceed under mild conditions in the presence of catalytic quan
NEW ACHIEVEMENTS IN THE USE OF ZIRCONIUM COMPLEXES IN THE CHEMISTRY OF ORGANO-ALUMINIUM AND MAGNESIUM COMPOUNDS
Dzhemilev, U. M.
, p. 4333 - 4346 (1995)
This paper describes some applications of a new reaction of catalytic cyclometallation of α-olefins, norbornenes and their derivatives, and 1,2-disubstituted acetylenes with organomagnesium and organoaluminium compounds effected by zirconium catalysts, leading to a series of five and macrocyclic heterocycles containing magnesium and aluminium.
Unusual pathway of the tantalum-catalyzed carboalumination reaction of alkenes with triethylaluminum
Sultanov, Rifkat M.,Samoilova, Elena V.,Popod'Ko, Natal'Ya R.,Tulyabaev, Artur R.,Sabirov, Denis Sh.,Dzhemilev, Usein M.
, p. 6619 - 6623 (2013/11/19)
Carboalumination of 1-alkenes (1-hexene, 1-octene, 1-decene) with Et 3Al in the presence of catalytic amounts of TaCl5 results in a mixture of 2-(R-substituted)- and 3-(R-substituted)-n-butylaluminums (1:1 ratio) in total yields of 75-85%. The TaCl5-catalyzed reaction of bicyclo[2.2.1]hept-2-ene, endo-tricyclo[5.2.1.02,6]deca-3,8-diene, and (exo/endo)-5-methylbicyclo[2.1.1]hept-2-ene with Et3Al leads to the formation of diethyl[2-exo-(2′-norbornylethyl)]aluminums in high yields. DFT calculations confirm the thermodynamic preference of the final exo product. The multistep reaction mechanisms for the formation of the resultant organoaluminums through tantalacyclopentanes as key intermediates are also discussed.
Synthetic applications of α-hydroxydiazenes. III. Uncatalyzed and phenol catalyzed hydroalkylation of alkenes and of azobenzene with alkylazodiphenylmethanols
Yeung, Dominic W. K.,Warkentin, John
, p. 2386 - 2394 (2007/10/02)
Alkylazodiphenylmethanols (C6H5)2C(OH)N=NR, (R = CH(CH3)2, CH2CH3, CH3), when decomposed in the presence of olefinic substrates or in the presence of azobenzene, hydroalkylate those substrates.Addition of R and H across the double bond of an unsymmetric alkene occurs with the regiochemistry expected for a radical mechanism, in which the grooup R adds first.Radical intermediates from decomposition of alkylazodiphenylmethanols have been demonstrated earlier with spin trapping experiments.The fact that addition of phenol can enhance the yield of hydroalkylation product suggests that the process is a radical chain reaction, with chain carrying steps consisting of the reactions: (i) R. + CH2=CHY -> RCH2C.HY (ii) RCH2C.HY + (C6H5)2C(OH)N2R -> RCH2CH2Y + (C6H5)2CO + N2 + R..One deuterioalkylation and some yield-optimizing experiments are also reported.
