Development of Immobilized Carreira (Phosphoramidite, Olefin) Ligands and Application in Iridium-Catalyzed Asymmetric Allylic Amination

A family of polystyrene-supported (phosphoramidite, olefin) ligands L1-L 4 , based on the original design by Defieber and Carreira, has been developed and applied in iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols (27 examples, up to 99% ee). Among them, functional resins L1 and L4 exhibit important advantages such as easy preparation, ligand recyclability, and easy handling for sequential use. As a distinctive advantage, the catalytic use of the iridium complexes of L1 and L4 allows the straightforward reuse of a high percentage of the expensive iridium metal involved in the complexes, which is not achievable under homogeneous conditions with the corresponding monomeric complexes.

Automated summary

A family of polystyrene-supported ligands based on the design of Defieber and Carreira were developed and successfully applied in the iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols, resulting in 27 examples with up to 99% enantiomeric excess. Two functional resins, L1 and L4, demonstrated significant advantages including easy preparation, ligand recyclability, and convenient handling for sequential use. Notably, the catalytic use of iridium complexes of L1 and L4 allowed for the efficient reuse of expensive iridium metal, which is not achievable under homogeneous conditions with monomeric complexes.