Series of chiral palladium(II) allyl and cinnamyl complexes bearing a C 1 -symmetric N-heterocyclic carbenes were synthesized from achiral precursors. The chirality of theses complexes results from the formation of the carbene-palladium bond which restricts the rotation of dissymmetric N-aryl substituents of the NHC and thus creates an axis of chirality. Chiral HPLC at preparative scale enabled the resolution of racemic complexes and provided a straightforward access to complexes with excellent enantiopurities (> 99.5% ee). Enantiopure complexes were studied by crystal X-ray diffraction and electronic circular dichroism (ECD). Their configuration stabilities were investigated both experimentally and theoretically through the determination of the rotational barrier values. These complexes were tested for the intramolecular α-arylation of amides, with a moderate chiral induction (up to 54% ee).

Construction of a bifunctional heterogeneous catalyst through the immobilization of palladium nanoparticles within ethylene-bridged chiral ruthenium/diamine-functionalized periodic mesoporous organosilica is developed. Structural analyses and characterizations show its well-defined chiral singlesite ruthenium species, and electron microscopy reveals its ordered mesostructure. As a bifunctional catalyst, it enables an efficient asymmetric transfer hydrogenation-Sonogashira coupling one-pot enantioselective tandem reaction, where Ru-catalysed asymmetric transfer hydrogenation followed by Pd-catalysed Sonogashira coupling affords various chiral conjugated alkynols in high yields with up to 97% enantioselectivity. As presented in this study, uniformly distributed palladium nanoparticles, high ethylene-bridged hydrophobicity, and single-site chiral ruthenium catalytic nature make a synergistic contribution to its catalytic performance. Furthermore, the high stability of palladium nanoparticles within its organosilicate network promotes high recyclability, and it could be used for the asymmetric transfer hydrogenation-Sonogashira coupling one-pot enantioselective tandem reaction of 4-iodoacetophenone and ethynylbenzene at least seven times without loss of its catalytic activity.

Utilization of amphiphilic poly(ethylene glycol) monomethyl ether modified hyperbranched polyethoxysiloxane as a support for the construction of bifunctional heterogeneous catalysts enables a highly efficient catalytic system thanks to its amphiphilic nature in aqueous organic transformations. Herein, through a three‐component self‐assembly procedure, we incorporate palladium/phosphine and chiral ruthenium/diamine functionality within poly(ethylene glycol) monomethyl ether modified hyperbranched polyethoxysiloxane, fabricating a multiple functionalized polyethoxysiloxane based mesoporous material. Structural analyses and characterizations disclose that well‐defined dual single‐site active centers are distributed uniformly within monodisperse mesoporous silica nanoparticles. As a bifunctional heterogeneous catalyst, this material performs the one‐pot enantioselective tandem reaction of Pd‐catalyzed Suzuki cross‐coupling and Ru‐catalyzed asymmetric transfer hydrogenation, affording various chiral biaryl alcohols with high yields and up to 99 % enantioselectivity. Furthermore, the catalyst can be recovered and recycled eight times without loss of its catalytic activity, demonstrating the practicability of the preparation of optically pure biaryl alcohols in one‐pot organic transformation.

A set of 16 chiral ruthenium complexes containing atropisomerically stable N-Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring-opening-cross metathesis (AR-OCM), the most effective chiral atrop BIAN-NHC Ru-catalyst (up to 97 : 3 er) was then converted to a Z-selective catechodithiolate complex. The latter proved to be highly efficient in Zselective AROCM of exo-norbornenes affording valuable transcyclopentanes with excellent Z-selectivity (> 98 %) and high enantioselectivity (up to 96.5 : 3.5 er).