Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes

Beilstein J Org Chem. 2016 Mar 2:12:406-12. doi: 10.3762/bjoc.12.43. eCollection 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 (1)H, (13)C, and (31)P spectroscopy.

Keywords: Dzhemilev reaction; aluminacyclopentanes; molybdenum complexes; phospholanes; zirconium complexes.