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The asymmetric synthesis of six-membered cyclic sulfamides via palladium-catalyzed alkene carboamination reactions of N-homo­allylsulfamides with aryl halides is described. High levels of enantio­selectivity were obtained with a catalyst composed of Pd2dba3 and (S)-Siphos-PE.

The development of palladium-catalyzed carboetherification andcarboamination reactions between aryl or alkenyl halides and alkenesbearing pendant heteroatoms is described. These transformationseffect the stereoselective construction of useful heterocycles,such as tetrahydrofurans, pyrrolidines, imidazolidin-2-ones, isoxazolidines,and piperazines. The scope, limitations, and applications of thesereactions are presented, and current stereochemical models are described.The mechanism of the product formation, which involves an unusualintramolecular SYN-insertion of an alkene intoa palladium-heteroatom bond, is also discussed in detail. 1 Introduction 2 Palladium-Catalyzed Synthesis of Tetrahydrofurans from γ-Hydroxyalkenesand Aryl or Alkenyl Halides 2.1 Mechanism of the Tetrahydrofuran Formation 3 Palladium-Catalyzed Synthesis of Pyrrolidines from γ-Aminoalkenesand Aryl or Alkenyl Halides 3.1 Tandem Palladium-Catalyzed N-Arylation-CarboaminationReactions of Primary Amines 3.2 Palladium-Catalyzed Carboamination Reactions of N-Protected γ-Aminoalkenes 3.3 Mechanism of the Palladium-Catalyzed Carboamination Reactions:Surprises and Utility 3.4 Application of the Palladium-Catalyzed Carboamination of N-Protected γ-Aminoalkenesto the Stereoselective Synthesis of (+)-Preussin and ItsAnalogues 4 Synthesis of Imidazolidin-2-ones via Palladium-Catalyzed CarboaminationReactions 5 Synthesis of Isoxazolidines via Palladium-Catalyzed CarboetherificationReactions 6 Synthesis of Piperazines via Palladium-Catalyzed CarboaminationReactions 7 Summary and Future Outlook