Pd- and Mo-Catalyzed Asymmetric Allylic Alkylation

Abstract

The ability to control the alkylation of organic substrates becomes ever more powerful by using metal catalysts. Among the major benefits of metal catalysis is the possibility to perform such processes asymmetrically using only catalytic amounts of the chiral inducing agent which is a ligand to the metal of the catalyst. A unique aspect of asymmetric metal catalyzed processes is the fact that many mechanisms exist for stereoinduction. Furthermore, using the same catalyst system, many types of bonds including but not limited to C-C, C-N, C-O, C-S, C-P, and C-H can be formed asymmetrically. An overview of this process using palladium and molybdenum based metals being developed in my laboratories and how they influence strategy in synthesizing bioactive molecular targets is presented.

Highly Enantioselective, Base‐Free Synthesis of α‐Quaternary Succinimides through Catalytic Asymmetric Allylic Alkylation

“…The absolute configuration of the newly formed quaternary center was later confirmed by single crystal X‐ray analysis of compound 5 g (see structure in Table ). As a matter of fact, this stereoselectivity could have also been predicted using the model proposed by Trost et al . where the enolate approaches the π‐allyl palladium‐( R , R )‐ L1 complex by its Re ‐face to avoid any disfavored steric interaction between the “wall” of the ligand and the amide moiety of the substrate (Figure ).…”

Metal catalyzed allylic alkylation: its development in the Trost laboratories

“…It is also the stimulus to see what other metals can do in catalytic allylic alkylations. In our labs, we have explored a number of metals, including molybdenum, 145 tungsten, 146 and ruthenium. 147 These metal catalysts favor bond formation to the more substituted allyl terminus.…”

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.…”