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 

机构地区：[1]Department of Chemistry,National University of Singapore,Singapore 117543 [2]Department of Materials Science,Fudan University,Shanghai 200438 [3]Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 350207

出　　处：《CCS Chemistry》2021年第5期1445-1452,共8页中国化学会会刊（英文）

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).

摘　　要：Cycloarenes are an essential class of polycyclic aromatic hydrocarbons with unique electronic structure,but their synthesis is very challenging.Herein,we report a facile synthetic strategy primarily involving macrocyclization by the Suzuki coupling reaction,followed by bismuth(III)triflate-catalyzed cyclization of vinyl ethers.By 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 8.Bond 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 measurements.Our method opens opportunities to access various expanded and core-modified cycloarenes in the future.

关 键 词：polycyclic aromatic hydrocarbon cycloarene kekulene octulene AROMATICITY 

分 类 号：O62[理学—有机化学]