ビス(シクロオクタジエン)ニッケル

用途有機合成用触媒

使用Bis(1,5-cyclooctadiene)nickel(0) is used as a catalyst for the cycloaddition of 1,3-dienes and is used to catalyze the addition of allyl phenyl sulfide to alkynes leading to 1,4-dienes. Also, it is involved as a catalyst for asymmetric alpha-arylation and heteroarylation of ketones with chloroarenes, stereoselective borylative ketone-diene coupling, cycloaddition of benzamides with internal alkynes and methyl carboxylation of homopropargylic alcohols.

一般的な説明Yellow crystals or yellowish green solid.

製造方法Bis(1,5-cyclooctadiene)nickel(0) is prepared by reduction of anhydrous nickel(II) acetylacetonate in the presence of the diolefin:Ni(acac)2 + 2 cod + 2 AlEt3 → Ni(cod)2 + 2 acacAlEt2 + C2H6 + C2H4Ni(cod)2 is moderately soluble in several organic solvents. One or both 1,5-cyclooctadiene ligands are readily displaced by phosphines, phosphites, bipyridine, and isocyanides. If exposed to air, the solid oxidizes to nickel(II) oxide. As a result, this compound is generally handled in a glovebox.

純化方法It is available in sealed ampoules under N2. All procedures should be carried out in a dry box and in an atmosphere of N2 or Argon in subdued light because the complex is light and oxygen sensitive, and flammable. The solid is washed with dry Et2O (under Ar) and separates from toluene as yellow crystals. Filter this under Ar gas pressure, place the crystals in a container and dry under a vacuum of 0.01mm to remove adhered toluene, flush with Ar and seal them under Ar or N2 in glass ampoules. [Semmelhack Org Reactions 19 115 and 178 1972, Wilke et al. Justus Liebigs Ann Chem 699 1 1966, Wender & Jenkins J Am Chem Soc 111 6432 1989, Fieser & Fieser Reagents for Org Synth 4 33, 16 29, 17 32.] SUSPECTED CARCINOGEN.