253123-54-5Relevant academic research and scientific papers
Synthesis and transformations of metallacycles 32. Novel method for the synthesis of cyclopentanols from aluminacyclopentanes
Dzhemilev,Ibragimov,Khafizova,Gilyazev,D'yakonov
, p. 133 - 136 (2004)
Cyclopentanols were synthesized by a one-pot method involving Cp2ZrCl2-catalyzed cycloalumination of α-olefins with trialkylalanes followed by the in situ reactions of aluminacyclopentanes with esters in the presence of catalytic amounts of Cu, Ni or Pd salts and complexes.
Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes
D'Yakonov, Vladimir A.,Makhamatkhanova, Alevtina L.,Agliullina, Rina A.,Dilmukhametova, Leisan K.,Tyumkina, Tat'Yana V.,Dzhemilev, Usein M.
supporting information, p. 406 - 412 (2016/04/05)
An efficient one-pot process for the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes was developed. The method involves the replacement of aluminium in aluminacyclopentanes, prepared in situ by catalytic cycloalumination of α-olefins and α,ω-diolefins, by phosphorus atoms on treatment with dichlorophosphines (R'PCl2). Hydrogen peroxide oxidation and treatment with S8 of the synthesized phospholanes and α,ω-bisphospholanes afforded the corresponding 3-alkyl(aryl)-1-alkyl(phenyl)phospholane 1-oxides, 3-alkyl(aryl)-1-alkyl(phenyl)phospholane 1-sulfides, bisphospholane 1,1'-dioxides, and bisphospholane 1,1'- disulfides in nearly quantitative yields. The complexes LMo(CO)5 (L = 3-hexyl-1-phenylphospholane, 3-benzyl-1-methylphospholane, 1,2-bis(1-phenylphospholan-3-yl)ethane, and 1,6-bis(1-phenylphospholan-3-yl)hexane were prepared by the reaction of 3-substituted phospholanes and α,ω-bisphospholanes with molybdenum hexacarbonyl. The structure of the complexes was proved by multinuclear 1H, 13C, and 31P spectroscopy.
The efficient method for the preparation of alkenylsilanes from organoaluminums
Kadikova, Rita N.,Zosim, Tat'Yana P.,Dzhemilev, Usein M.,Ramazanov, Ilfir R.
, p. 14 - 19 (2014/05/20)
Silyl esters of sulfonic acids are convenient and efficient silylating agents for β,β- and β-substituted 1-alkenylaluminums. The reaction proceeds at room temperature in CH2Cl2 or hexane for 18 h to give corresponding alkenylsilanes in high yield. At the same time, α,β-disubstituted and α,β,β-trisubstituted 1-alkenylaluminums were inert in the reaction under study. The reaction with aluminacyclopen-2-enes and aluminacyclopentanes takes place on the less sterically hindered reaction center. Using electron-donating solvents (diethyl ether, THF) inhibits the reaction. A new convenient procedure of silylation was developed, which consists in obtaining the silyl tosylate by the reaction of chlorosilanes with anhydrous sodium tosylate in toluene solution. The resulting reaction mixture was reacted with organoaluminum compounds without isolation of silyl tosylate.
Synthesis and conversions of metallocycles 22. NMR studies of the mechanism of Cp2ZrCl2-catalyzed cycloalumination of olefins with triethylaluminum to form aluminacyclopentanes
Khalilov,Parfenova,Rusakov,Ibragimov,Dzhemilev
, p. 2051 - 2058 (2007/10/03)
The mechanism of cycloalumination of olefins under the action of AlEt3 in the presence of Cp2ZrCl2 giving rise to aluminacyclopentanes was investigated by dynamic 1H and 13C NMR spectroscopy. The bimetallic complex Cp2ZrEtCl-AlEt3 is formed initially and is converted into the bridged complex Cp2Zr(Cl)CH2CH2AlEt2 as a result of β-hydride shift and elimination of the ethane molecule. The resulting complex adds a molecule of the initial olefin yielding aluminacyclopentanes. Under the action of Et2AlCl in the presence of an excess of AlEt3, zirconacyclopentanes give rise to intermediate bimetallic complexes stable at -70 °C. Under the reaction conditions, the latter compounds are converted into aluminacyclopentanes.
