Mantis-shaped Bifunctional Chiral Monodentate-Type Phosphine Ligands: Application in Pd-Catalyzed Asymmetric Allylic Substitutions
Jin Liu , Bo-Wen Pan , You-Ping Tian , Ying Ge , Xiong-Li Liu , Min Zhang , Ying Zhou , Yang Shi
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (24) : 3529 -3534.
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.
OPI-Phos ligands / Mantis-shape / Monodentate / Phosphine ligands / Bifunctional / Monochiral arm / Asymmetric allylic substitutions / Heterocycles
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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