Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates

Abstract

The concept of merging enamine activation catalysis with transition metal catalysis is an important strategy, which allows for selective chemical transformations not accessible without this combination. The amine catalyst activates the carbonyl compounds through the formation of a reactive nucleophilic enamine intermediate and, in parallel, the transition metal activates a wide range of functionalities such as allylic substrates through the formation of reactive electrophilic π-allyl-metal complex. Since the first report of this strategy in 2006, considerable effort has been devoted to the successful advancement of this technology. In this chapter, these findings are highlighted and discussed.

Multifunctional chiral aminophosphines for enantiodivergent catalysis in a palladium‐catalyzed allylic alkylation reaction

“…This atom economic mode of asymmetric catalysis, however, is also very challenging in reaction design in both metal‐catalyzed and organocatalyzed processes. Interestingly, given that the combination of metal catalysis and organocatalysis is a rapidly developing field, 2–4 in which an organocatalyst can serve as either a catalyst or a ligand, exploring enantiodivergent catalysis in this hybrid mode of catalysis may present new opportunities in finding cooperative catalytic modes. Here, we report an enantiodivergent catalysis in a Pd‐catalyzed asymmetric allylic alkylation (AAA) reaction, induced by a multifunctional chiral phosphine ligand.…”

Combining Palladium and Chiral Organocatalysis for the Enantioselective Deconjugative Allylation of Enals via Dienamine Intermediates

“…While recent years have seen the combination of enamine- and metal-catalysis facilitate access to novel synthetic building blocks, examples of cooperative dienamine- and metal-catalysis are rare . In contrast to organocatalytic reactions involving enamine intermediates, there is no uniform model for catalyst control of regio- or enantioselectivity in reactions of dienamine intermediates, which likely contributes to the dearth of metal cocatalyzed asymmetric transformations of the latter.…”