Abstract
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 n-butyllithium to zirconocene dichloride conveniently produces a zirconocene equivalent, i.e., “Cp2Zr”, 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.
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