title: Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes.
abstract: 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 (1)H, (13)C, and (31)P spectroscopy.
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: D'yakonov
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Alevtina L
authors.initials: AL
authors.lastname: Makhamatkhanova
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Rina A
authors.initials: RA
authors.lastname: Agliullina
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Leisan K
authors.initials: LK
authors.lastname: Dilmukhametova
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Tat'yana V
authors.initials: TV
authors.lastname: Tyumkina
authors.affiliation: Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, Ufa 450075, Russian Federation.
authors.forename: Usein M
authors.initials: UM
authors.lastname: Dzhemilev
keywords: Dzhemilev reaction; aluminacyclopentanes; molybdenum complexes; phospholanes; zirconium complexes