Facile Synthesis of Aryl-Substituted Cycloarenes via Bismuth(III)Triflate-Catalyzed Cyclization of Vinyl Ethers

作     者：Wei Fan Yi Han Shaoqiang Dong Guangwu Li Xuefeng Lu Jishan Wu 

作者机构：Department of ChemistryNational University of SingaporeSingapore 117543 Department of Materials ScienceFudan UniversityShanghai 200438 Joint School of National University of Singapore and Tianjin UniversityInternational Campus of Tianjin UniversityFuzhou 350207 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2021年第3卷第5期

页      面：1445-1452页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：The authors acknowledge financial support from the MOE Tier 3 program(no.MOE2014-T3-1-004) Tier 2 grant(no.MOE2018-T2-2-094) NRF Investigatorship(no.NRF-NRFI05-2019-0005) 

主　　题：polycyclic aromatic hydrocarbon cycloarene kekulene octulene aromaticity 

摘      要：Cycloarenes are an essential class of polycyclic aromatic hydrocarbons with unique electronic structure,but their synthesis is very ***,we report a facile synthetic strategy primarily involving macrocyclization by the Suzuki coupling reaction,followed by bismuth(III)triflate-catalyzed cyclization of vinyl *** utilizing this approach,aryl-substituted soluble cycloarenes 7 and 8 with different sizes were obtained.X-ray crystallographic analysis revealed a slightly distorted backbone in the kekulene derivative 7 and a saddle-shaped skeleton in the octulene derivative *** length analysis suggested that both of the cycloarenes mainly complied with the Clar’s bonding model with dominant local aromaticity,which was also in accord with our NMR measurements and the theoretical calculations[nucleus-independent chemical shift[NICS],anisotropy of the induced current density(ACID),three-dimensional isochemical shielding surface(3D ICSS)].The optical properties were investigated by UV-Vis absorption and fluorescence spectral *** method opens opportunities to access various expanded and core-modified cycloarenes in the future.