Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically-Formed Chiral Auxiliary

Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited either in terms of efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process

Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary

Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited in terms of either efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/ hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process

Palladium-Catalyzed Functionalization of Olefins and Alkynes: From Oxyalkynylation to Tethered Dynamic Kinetic Asymmetric Transformations (DYKAT)

This review presents an account of the palladium-catalyzed functionalizations of alkenes and alkynes developed at the Laboratory of Catalysis and Organic Synthesis (LCSO). Starting from the intramolecular oxy- and aminoalkynylation of alkenes, tethered methods were then developed to functionalize allylic amines and alcohols, as well as propargylic amines. Finally, a new dynamic kinetic asymmetric transformation was developed based on the use of a 'one-arm' Trost-type ligand, giving access to enantiopure amino alcohols. Each section is a personal account by the researcher(s) who performed the work. 1 Introduction, 2 Oxy- and Aminoalkynylation of Olefins, 3 In Situ Tethering Strategies for the Synthesis of Vicinal Amino Alcohols and Diamines, 4 Carboamination of Allylic Alcohols, 5 Carbooxygenation of Propargylic Amines, 6 Enantioselective Carboetherification/Hydrogenation via a Catalytically Formed Chiral Auxiliary, 7 Conclusio