21078-65-9Relevant academic research and scientific papers
Diastereoselective synthesis of functionally substituted alkene dimers and oligomers, catalysed by chiral zirconocenes
Kovyazin, Pavel V.,Abdullin, Il'giz N.,Parfenova, Lyudmila V.
, p. 144 - 152 (2018/11/21)
The research addresses the reaction of terminal alkenes and propene with AlR3 (R = Me, Et) in the presence of chiral Zr complexes, rac-[Y(η5-C9H10)2]ZrCl2 (Y = C2H4, SiMe2) or (NMI)2ZrCl2 (NMI- η5–neomenthylindenyl), and methylaluminoxane. The effect of reaction conditions, catalyst and trialkylalane structure on the substrate conversion and the reaction chemo- and stereoselectivity has been studied. The reaction predominantly goes via the stage of alkene methyl(ethyl)zirconation with subsequent introduction of substrate molecules into the Zr-C bond. As a result, a diastereoselective one-pot method for the synthesis of functionally substituted linear terminal alkene dimers and propene oligomers was developed.
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.
supporting information, 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.
