Stereoselective Synthesis of Saturated Heterocycles via Palladium-Catalyzed Alkene Carboetherification and Carboamination Reactions

The development of palladium-catalyzed carboetherification and carboamination reactions between aryl or alkenyl halides and alkenes bearing pendant heteroatoms is described. These transformations effect the stereoselective construction of useful heterocycles, such as tetrahydrofurans, pyrrolidines, imidazolidin-2-ones, isoxazolidines, and piperazines. The scope, limitations, and applications of these reactions are presented, and current stereochemical models are described. The mechanism of the product formation, which involves an unusual intramoleculars syn-insertion of an alkene into a palladium-heteroatom bond, is also discussed in detail.