Comprehensive Summary 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.
Jin et al. (2025) studied this question.