文献类型：期刊文献

英文题名：Antiaromatic Sapphyrin Isomer: Transformation into Contracted Porphyrinoids with Variable Aromaticity

作者：Li, Qizhao[1,2];Ishida, Masatoshi[3];Wang, Yunyun[1,2];Li, Chengjie[1,2];Baryshnikov, Glib[5];Zhu, Bin[1,2];Sha, Feng[1,2];Wu, Xinyan[1,2];agren, Hans[6];Furuta, Hiroyuki[4];Xie, Yongshu[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Joint Int Res Lab Precis Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Tokyo Metropolitan Univ, Grad Sch Sci, Dept Chem, Tokyo 1920397, Japan;[4]Kyushu Univ, Grad Sch Engn, Dept Appl Chem, Fukuoka 8190395, Japan;[5]Linkoping Univ, Dept Sci & Technol, Lab Organ Elect, S-60174 Norrkoping, Sweden;[6]Uppsala Univ, Dept Phys & Astron, S-75120 Uppsala, Sweden

年份：2023

卷号：62

期号：1

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20224913216264);WOS:【SCI-EXPANDED(收录号:WOS:000916483000001)】；

基金：This work at ECUST was financially supported by the Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the International Cooperation Program of Shanghai Science and Technology Committee (17520750100), NSFC (22131005, 21971063, 22201074, 22075077), Program of Introducing Talents of Discipline to Universities (B160170), the Fundamental Research Funds for the Central Universities (222201717003), and Program of Shanghai Academic Research Leader (20XD1401400). The work in TMU was supported by a JST PREST (JPMJPR2103), and in Kyushu was endorsed by a Grants-in-Aid (JP20H00406, JP21 K18984) from the Japan Society for the Promotion of Science (JSPS). G. B. thanks for the Swedish National Infrastructure for Computing (SNIC) resources at the High-Performance Computing Center North (HPC2 N) and the financial support of the Swedish Research Council (2018-05973, 2020-04600). The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for compound characterization.

语种：英文

外文关键词：Antiaromaticity; N-Confused Porphyrin; Porphyrinoids; Sapphyrin; Skeletal Rearrangement

摘要：Sapphyrin is a pentapyrrolic expanded porphyrin with a 22 pi aromatic character. Herein, we report the synthesis of a 20 pi antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P-5 with a terminal beta-linked pyrrole. The resulting isomer 1, containing a mis-linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro-carbon-containing [5.6.5.6]-tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone-appended N-confused corrole 3, and thermal fusion gave a [5.6.5.7]-tetracyclic-ring-embedded 14 pi aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis-linked pyrrole moiety of P-5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity.