Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates

Abstract

The transition metal-catalyzed allylic substitution of unactivated allylic substrates (allylic alcohols, allylic ethers and allylic amines) is rapidly becoming an important area of research. There are several advantages to using these substrates in allylic substitution reactions: the use of unactivated alcohols minimizes the production of waste by-products and reaction steps; and allylic ethers and allylic amines are useful substrates because of their stability and their presence in numerous biologically active compounds. Research in this field has therefore gained widespread attention for promoting the development of efficient and environmentally benign procedures for the formation of C-C, C-N and C-O bonds.

Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations

“…This particular subset has found numerous applications and has been reviewed periodically. 178,179,180,181 As such, a limited number of examples are presented here for illustration and the reader is advised to consult previous reviews dedicated to this topic for more information.…”

Palladium Catalyzed Asymmetric Three-Component Coupling of Boronic Esters, Indoles, and Allylic Acetates

“…The process could be rendered stereo selective with appropriate ligands on palladium to differentiate the faces of the indole nucleophile and the termini of the π-allyl electrophile. 12 …”

Synthesis of Enantiopure γ‐Lactones via a RuPHOX‐Ru Catalyzed Asymmetric Hydrogenation of γ‐Keto Acids

“…[12] However, harsh reaction conditions (100 atm) and a long reaction time (110 h) were needed to ensure the completion of the reaction. [15][16] Specifically, RuPHOXÀRu has been employed as an efficient enantiopure catalyst in several asymmetric hydrogenations with excellent asymmetric catalytic behavior. [13a] Although excellent enantioselectivities were obtained, a long reaction time was still needed.…”