253123-53-4Relevant academic research and scientific papers
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.
, p. 406 - 412 (2016)
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.
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.
