Advances in the Intermolecular Asymmetric Allylic Functionalization of Unreactive Acyclic Alkenes

Allylic C(sp 3)–H functionalized architectures are not only widely present in natural products, pharmaceuticals, and functional organic materials, but also serve as versatile building blocks to furnish important functionalized molecules in synthetic chemistry. Accordingly, various strategies to access allylic functionalized alkenes in a stereoselective manner have been developed. However, chemo-, regio- and stereoselective intermolecular asymmetric allylic functionalization (AAF) of unreactive acyclic alkene (UAA) from readily available materials, representing a highly atom- and step-economic approach toward the generation of structural complexity, remains elusive and challenging. Herein, we review all intermolecular asymmetric catalyzed methods, with emphasis on the construction of chiral allylic units by activation of allylic C–H bonds of UAAs. Our analysis serves to document the considerable and rapid progress within the field, while also highlighting the limitations of current methods. 1 Introduction 2 Asymmetric Allylic Oxygenation 3 Asymmetric Allylic Amination 4 Asymmetric Allylic Carbonization 5 Asymmetric Allylic Sulfuration 6 Conclusion and Outlook