Stereoselective Self-Assembly of Chiral Metalla[2]Catenanes and Lemniscular Macrocycles  

作　　者：Shu-Jin Bao Hai-Ning Zhang Guo-Xin Jin 

机构地区：[1]Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,State Key Laboratory of Molecular Engineering of Polymers,Department of Chemistry,Fudan University,Shanghai 200433

出　　处：《CCS Chemistry》2024年第8期2000-2010,共11页中国化学会会刊（英文）

基　　金：the National Science Foundation of China(grant nos.22031003 and 21720102004);the Shanghai Science Technology Committee,China(grant no.19DZ2270100);the Shanghai Post-doctoral Excellence Program,China(grant no.2022009).

摘　　要：Designing and stereoselectively constructing chiral mechanically interlocked molecules(MIMs)is a goal that many chemists are pursuing due to their potential in the development of functional molecular machines involved in catalysis,sensing,and chiroptical switching.However,the synthesis of enantiopure supramolecular entities with crystallographic structures remains challenging.Herein,the stereoselective self-assembly of chiral metalla[2]catenanes interlocked by two D-shaped macrocycles was realized by combining long binuclear half-sandwich organometallic Cp*Rh^(III)(Cp*=η^(5)-pentamethylcyclopentadienyl)clip and ditopic monodentate ligand incorporating L-leucine residues.The resulting metalla[2]catenane displayed unique co-conformational mechanical helical chirality characteristics arising from the chirality transfer of the chiral ligand.Furthermore,decreasing the length of the binuclear Cp*Rh^(III)clip and adjusting the steric hindrance of the amino-acid side chains(L-alanine and L-phenylalanine)in the ligands resulted in two lemniscular macrocycles with left-handed(M)-twisted conformational chirality.To the best of our knowledge,the synthesized macrocycles are the first family of homochiral abnormal lemniscate-shaped organometallic macrocycles featuring figure-eight geometries.Metalla[2]catenanes and macrocycles with opposite chirality were also generated by employing corresponding D-amino acid ligands,as evidenced by single-crystal X-ray diffraction,nuclear magnetic resonance,mass,and circular dichroism spectroscopies.Our present study demonstrates that homochiral MIMs can be accessed readily using amino acid–containing ligands through rational molecular design.

关 键 词：stereoselective synthesis CHIRALITY catenanes twisted macrocycles aminoacid residues 

分 类 号：O62[理学—有机化学]