Asymmetric Assisted Tandem Catalysis: Hydroamination followed by Asymmetric Friedel–Crafts Reaction from a Single Chiral N,N,N′,N′‐Tetradentate Pyridylmethylamine‐Based Ligand

With the rising interest in asymmetric catalysis promoted by earth-abundant elements, a chiral ligand will undoubtedly be the most valuable unit of the catalyst. The first proof of concept of the use of a multitask chiral ligand in an asymmetric assisted tandem catalysis protocol that successively combines metallo- and organocatalytic processes is reported herein. In this protocol, the chiral ligand of the newly designed rare-earth catalyst of the first reaction is converted into a novel chiral organocatalyst for the second transformation by the simple addition of HCl. The observation of some enantioinduction in the tandem sequencealkyne hydroamination followed by enantioselective Friedel-Crafts alkylationconfirms the relay of the chiral N,N,N,N-tetradentate ligand and the importance of its pyridylmethylamine scaffold.