The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifu...The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifunctional chiral monodentate-type phosphine ligands having octahydroindole-imidazolone skeleton as the key stereodirecting monochiral arm and the tertiary amine group as an H-bond acceptor,namely OPI-Phos ligands,which were prepared from the optically pure easily accessible octahydroindole-amides in one step.These ligands are characteristic of easy synthesis,rigid backbone,high tunability and air stability.They were proven to be a class of efficient chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions of rac-allyl acetates with O and C-nucleophiles,achieving high reactivity and enantioselectivity.Single crystal structure of OPI-Phos ligand/palladium complexes revealed a possible monodentate manner-type reaction mechanism.展开更多
基金Guizhou Provincial Science and Technology Support Program(QKHS[2025]110)Guizhou Provincial Basic Research Program(ZK[2024]374,ZK[2023]404 and ZK[2024]370)the Guiyang City Science and Technology Plan Project([2024]2-37).
文摘The noncovalent interaction-assisted transition metal catalysis has attracted intense interest,and emerged as a powerful tool to develop new privileged ligands.Herein,we developed a library of novel mantis-shaped bifunctional chiral monodentate-type phosphine ligands having octahydroindole-imidazolone skeleton as the key stereodirecting monochiral arm and the tertiary amine group as an H-bond acceptor,namely OPI-Phos ligands,which were prepared from the optically pure easily accessible octahydroindole-amides in one step.These ligands are characteristic of easy synthesis,rigid backbone,high tunability and air stability.They were proven to be a class of efficient chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions of rac-allyl acetates with O and C-nucleophiles,achieving high reactivity and enantioselectivity.Single crystal structure of OPI-Phos ligand/palladium complexes revealed a possible monodentate manner-type reaction mechanism.
