二核パラジウム触媒によるC-H結合のアルキンへの付加反応
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概要
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A novel binucleating ligand, <I>N</I>, <I>N</I>-bis [2-(diphenylphosphino) phenyl] formamidine (Hdpfam) has been prepared and utilized for the synthesis of dinuclear palladium complexes Pd<SUB>2</SUB>R<SUB>2</SUB> (μ-X) (μ-dpfam) (R=Ar, Me, X=Cl, Br, I, OH).Hydroxo-bridged complexes Pd<SUB>2</SUB>R<SUB>2</SUB> (μ-OH) (μ-dpfam) served as catalyst for the <I>cis</I>-addition of aromatic C-H bonds to alkynes in the presence of catalytic amounts of tri-<I>n</I>-butylborane. In contrast to the Friedel-Crafts type reaction, electron-poor arenes also can be used for the addition reaction. In the reaction of monosubstituted arenes, meta isomers were main products in all cases. The addition of olefinic C-H bonds of indene to alkynes was also achieved by using chloro-bridged complexes Pd<SUB>2</SUB>R<SUB>2</SUB> (μ-Cl) (μ-dpfam) and LiAlH (OBu<SUP><I>t</I></SUP>)<SUB>3</SUB> as catalyst. The palladium complexes supported by dpfam catalyzed the cross-addition of triisopropylsilylacetylene to various internal and terminal unactivated alkynes, giving enynes in high yields.
- 社団法人 有機合成化学協会の論文
- 2007-12-01