Abstract

This account summarizes our recent work on palladacycles in organic synthesis and describes some unique catalytic properties of palladacycles as transition-metal catalysts for some useful transformations. Asymmetric induction has been realized by using chiral palladacycles as transition-metal catalysts. The influence of the C−Pd bond of palladacycles on their catalytic activity has been revealed. The reaction selectivity can be switched by appropriate choice of an sp<sup>2</sup>- or sp<sup>3</sup>-hybridized <i>C</i>,<i>P</i>-palladacycle catalyst. 1 Introduction 2 The Discovery of the Use of Palladacycles as Transition-Metal Catalysts and Their Applications in Asymmetric Catalysis 3 Switch Between Addition and Ring Opening in the Reaction of Oxabicyclic Alkenes with Terminal Alkynes by Catalysis with sp<sup>2</sup>-<i>C</i>,<i>P</i>- or sp<sup>3</sup>-<i>C</i>,<i>P</i>-Palladacycles 4 Synthesis of Polysubstituted Furans, Methylenecyclopropanes, and Polycyclic 5<i>H</i>-Benzo[<i>b</i>]azepines through Catalysis by Palladacycles 5 Conclusions

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