ジルコニウムを用いる有機合成-その後の展開
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概要
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Alkenylzirconium compounds react with various organic halides in the presence of a palladium or nickel catalyst to give the corresponding cross-coupling products in high yields with high selectivities. Carbometallation of alkynes using alkylaluminums such as trimethylaluminum is catalyzed by zirconocene dichloride. The triisobutylaluminum/zirconocene dichloride system induces hydrometallation and subsequent carbometallation of enynes to afford exocyclic olefins. Addition of 2 equiv. of <I>n</I>-butyllithium to zirconocene dichloride conveniently produces a zirconocene equivalent, i.e., “Cp<SUB>2</SUB>Zr”, which can induce bicyclization of enynes or diynes. Reactions of alkenes and alkynes with the zirconocene give zirconocene-alkene and-alkyne complexes, respectively, whose structures have been determined by X-ray studies. Novel 1, 2-migration reactions on zirconium or other metals are also discussed.