Inherently Chiral and Symmetrical Heteroatom-Doped Zigzag-Type Hydrocarbon Belts  

作　　者：Xue-Yuan Wang Xin-Yu Zhang Shuo Tong Qing-Hui Guo Mei-Ling Tan Cheng-Jun Li Mei-Xiang Wang 

机构地区：[1]Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology(Ministry of Education),Department of Chemistry,Tsinghua University,Beijing 100084

出　　处：《CCS Chemistry》2024年第5期1198-1210,共13页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(NSFC,grant nos.22050005,21920102001,22171160,and 22371161);Tsinghua University Dushi Program,and China National Postdoctoral Program for Innovative Talents(grant no.BX20220184).

摘　　要：hydrocarbon belts due to their potential applications in carbon nanotechnology.By contrast,heteroatomembedded zigzag hydrocarbon belts as advanced design strategies with fascinating structures and desirable,unique properties have remained largely unexplored,and inherently chiral ones are unknown.Herein,we report the synthesis of a diversity of symmetric and highly enantiopure inherently chiral O-and N-doped zigzag-type hydrocarbon belts starting from strainless macrocycles based on fjord-stitching strategy.The readily available pertriflated resorcin[6]arene underwent partial hydrolyses and intramolecular S_(N)Ar reactions to form a calix[3](9H-xanthene)derivative and a prochiral half-belt selectively.Straightforward transformations of calix[3](9H-xanthene)into C_(3v)-symmetric molecular belts were achieved by closing the rest of the fjords with triple intramolecular S_(N)Ar reactions and Yamamoto homo coupling reactions,as well as palladiumcatalyzed intermolecular acridination reactions with primary amines.The prochiral half-belt underwent enantioselective desymmetrizative mono-acridination to afford an inherently chiral N,O_(4)-bridged pseudo-belt with an enantiomeric excess(ee)value of>99%under the catalysis of Pd(OAc)_(2)and(R)-Antphos.Ring closure reactions of the pseudo-belt produced diverse heteroatom-inlayed zigzag-type hydrocarbon belts of inherent chirality.Further,we showed the unique cavity structures of the belts and demonstrated interesting chiroptic properties of the inherently enantiopure chiral belts.This research opens the door for the exploration of novel and sophisticated symmetric and inherently chiral molecular nanobelt structures with outstanding physical and chemical properties,as well as potential applications.

关 键 词：zigzag-type molecular belt HETEROCYCLE chiroptical property fjord-stitching strategy arene 

分 类 号：O62[理学—有机化学]