Binuclear Double-Stranded Helicates and Their Catalytic Applications in Desymmetrization of Mesodiols

The ligand L₁ of 4-methyl-2,6-diformylphenol and L₂ of 4- tert-butyl-2,6-diformylphenol are synthesized through Schiff base condensation with rac-, ( R)-(+), or ( S)-(-)-1,1'-binaphthyl-2,2'-diamine (BNDA). As a result, the racemic L₁^rac, L₂^rac, and enantiopure L₁^RR, L₁^SS, L₂^RR, and L₂^SS ligands are obtained incorporating Cu(II) and Zn(II) salts by a simple one-pot metal template method. The series of dinuclear complexes of [M₂LX₂] (here, M = Cu²⁺, Zn²⁺; X = acetate ion, chloride ion; L = L₁^RR, L₁^SS, L₁^rac, L₂^RR, L₂^SS, L₂^rac) formulas are obtained in common. Among them, the single crystal X-ray structures for [Zn₂L₁^rac(OAc)₂] and [Zn₂L₁^SSCl₂] complexes are obtained. The detailed crystal structure and the chiroptical studies performed on these complexes dictates a self-sorting behavior in their self-assembly process and illustrate a chirality transfer from the ligand to the metal center on the complexes. The enantiopure dinuclear complexes [M₂L^RRX₂] and [M₂L^SSX₂] generate enantiopure ΛΛ and ΔΔ isomers, respectively, but the racemic complexes produce only homochiral ΛΛ and ΔΔ assemblies. The detailed studies based on UFLC (Ultra Fast Liquid Chromatography), CD, and single crystal X-ray structure together show the absence of heterochiral ΛΔ mesocate. All these complexes are adapted as catalysts for desymmetrization of various mesodiols, and the enantiopure complexes are found to give efficient enantioselectivity in desymmetrization of mesodiols with benzoyl chloride to monobenzoylated ester providing 98% yield and 92% ee.