Recent Developments in Asymmetric Allylic Amination Reactions

The asymmetric synthesis of allylic amines is an important research area in modern synthetic organic chemistry, primarily due to the inherent utility and ubiquity of this functional group in various synthetic intermediates and bioactive agents. For instance, a plethora of methods for the stereocontrolled construction of allylic amines now provides a vibrant array of strategies for the installation of this important functionality. This review highlights developments in the field since 1998 through the provision of the most important methods and their mechanistic aspects in order to provide insight into their current scope and limitations. Hence, we envisage it will be an essential guide to the current state-of-the-art for this important area, which highlights potential new opportunities for further developments. 1 Introduction 2 Allylic Substitution 2.1 Transition Metal Catalyzed via a π-Allyl Intermediate 2.2 Lewis Base Catalyzed 2.3 Azametallation/Elimination 2.4 Miscellaneous 3 Sigmatropic Rearrangements 3.1 [3,3]-Rearrangement 3.2 [2,3]-Rearrangement 3.3 Curtius Rearrangement 4 Amination of Alkenes 4.1 Hydroamination 4.2 Carboamination 4.3 Diamination 5 Wacker-Type Oxidative Amination 6 C–H Functionalization 7 Electrophilic Amination 8 Conclusions