2価ルテニウム錯体触媒を用いるアルキン類の環化三量化反応

概要

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The catalytic intramolecular cyclotrimerization of alkynes with various unsaturated molecules were achieved using ruthenium (II) complexes bearing a cyclopentadienyl-type planar ligand as catalyst precursors.<BR>In the presence of a catalytic amount of the Ru (II) complex, a 1, 6-diyne reacted with norbornene to afford a novel tandem cyclopropanation product together with the expected [2+2+2] cycloadduct. On the other hand, the cycloaddition of the diynes with heterocycloalkenes or monoalkynes were catalyzed by pentamethylcyclopentadienylruthenium complexes at ambient temperature to give the desired [2+2+2] cycloadducts selectively. The synthesis of bicyclic pyridines was achieved by means of the Ru (II) -catalyzed cycloaddition of the 1, 6-diynes with electron-deficient nitriles or dicyanaides. Similarly, the cycloaddition with heterocumulenes such as isocyanates and isothiocyanates furnished bicyclic pyridones or thiopyran imines, respectively. The electron-deficient carbonyl group of some tricarbonyl compounds also participated in the cycloaddition with the 1, 6-diynes, but the expected 2<I>H</I>-pyran underwent electrocyclic ring opening to give rise to unsaturated carbonyl products.
社団法人有機合成化学協会の論文
2005-02-01