III International Conference

PP-II-46CYCLOALUMINATION OF α,ω-DIOLEFINS CATALYZED BY Cp 2 ZrCl 2 – NOVELROUTE TO MACRO CYCLIC COMPOUNDSKhafizova L.O., Gilyazev R.R., Ibragimov A.G., Dzhemilev U.M.Institute of Petrochemistry and Catalysis RAS, Ufa, RussiaE-mail: ink@anrb.ruThe interaction between 1,5-hexadiene and EtAlCl 2 (1:2) in the presence of Mg as anacceptor of halogenide ions and Cp 2 ZrCl 2 catalyst (10 mol %) in THF at ~ 20 o C led to1-ethyl-3,4-di(but-3-enyl)-aluminacyclopentane (1), 2,7-diethyltetradecahydrodialuminacyclopenta[a,e]cyclooctene(2) with two symmetrically annulated to cyclooctane ringaluminacyclopentane fragments and 2,7,12-triethylecosahydro-1H-trialuminacyclopenta[a,e,i]cyclododecene (3) with three symmetrically annulated to cyclododecane ringaluminacyclopentane fragments.Cycloalumination of 1,7-octadiene with EtAlCl 2 (two-fold excess) under the reactionconditions (Cp 2 ZrCl 2 (10 mol %), THF, 20 o C, 8 h) resulted in 1-ethyl-3,4-di(hex-5-enyl)aluminacyclopentane and cyclododecane with two symmetrically annulatedaluminacyclopentane fragments.The tested 1,9-decadiene and 1,11-dodecadiene come into the cycloalumination reactionwith EtAlCl 2 catalyzed by Cp 2 ZrCl 2 to produce selectively trans-3,4-disubstitutedaluminacyclopentanes in ~ 40–45 % yield.In accordance with previously reported work [1], stereoselective cycloalumination of α-olefins with EtAlCl2 in the presence of Mg and Cp2ZrCl2 catalyst was found to afford trans-3,4-dialkylsubstituted aluminacyclopentanes.We now discuss the new cycloalumination reaction of α,ω-diolefins with EtAlCl 2 in thepresence of catalytic amounts of Cp 2 ZrCl 2and carbocycles with annulated aluminacyclopentane fragments.and activated Mg giving aluminacyclopentanesIt was stated that the interaction between 1,5-hexadiene and EtAlCl 2 (1:2) in the presenceof Mg as an acceptor of halogenide ions and Cp 2 ZrCl 2 catalyst (10 mol %) in THF at ~ 20 o Cled to 1-ethyl-3,4-di(but-3-enyl)aluminacyclopentane (1), 2,7-diethyltetradecahydrodialuminacyclopenta[a,e]cyclooctene(2) with two symmetrically annulated to cyclooctanering aluminacyclopentane fragments and 2,7,12-triethylecosahydro-1Htrialuminacyclopenta[a,e,i]cyclododecene(3) with three symmetrically annulated tocyclododecane ring aluminacyclopentane fragments. The influence of catalyst concentration,the starting reagents ratio, temperature and duration of the reaction onto yield and formationselectivity of mono- (1), three- (2) and tetracyclic (3) organoaluminium compounds (OAC) isdiscussed (Scheme).247