文献类型：期刊文献

英文题名：Skeletal Rearrangement of Twisted Thia-Norhexaphyrin: Multiply Annulated Polypyrrolic Aromatic Macrocycles

作者：Li, Qizhao[1,2];Ishida, Masatoshi[3,4];Kai, Hiroto[3,4];Gu, Tingting[6];Li, Chengjie[1,2];Li, Xin[5];Baryshnikov, Glib[5];Liang, Xu[6];Zhu, Weihua[6];Agren, Hans[5];Furuta, Hiroyuki[3,4];Xie, Yongshu[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Kyushu Univ, Dept Chem & Biochem, Grad Sch Engn, Fukuoka 8190395, Japan;[4]Kyushu Univ, Ctr Mol Syst, Fukuoka 8190395, Japan;[5]KTH Royal Inst Technol, Dept Theoret Chem & Biol, Sch Biotechnol, S-10691 Stockholm, Sweden;[6]Jiangsu Univ, Sch Chem & Chem Engn, Zhenjiang 212013, Jiangsu, Peoples R China

年份：2019

卷号：58

期号：18

起止页码：5925

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20191406717114);WOS:【SCI-EXPANDED(收录号:WOS:000465413400019)】；

基金：This work at ECUST was financially supported by Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03) and the international Cooperation Program of Shanghai Science and Technology Committee (17520750100), NSFC (21772041, 21702062, 21811530005), and Program of Introducing Talents of Discipline to Universities (B160170). Part of the work in Kyushu was supported by Grants-in-Aid (JP15K13646 to H.F., JP16K05700, and JP17H05377 to M.I.) from the Japan Society for the Promotion of Science (JSPS). We acknowledged Prof. Fukatsu and Dr. Yasutake (Univ. Tokyo, Japan) for their help in the near IR emission measurement.

语种：英文

外文关键词：aromaticity; macrocycles; porphyrinoids; skeletal rearrangement

摘要：A hybrid thia-norhexaphyrin comprising a directly linked N-confused pyrrole and thiophene unit (1) revealed unique macrocycle transformations to afford multiply inner-annulated aromatic macrocycles. Oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone triggered a cleavage of the C-S bond of the thiophene unit, accompanied with skeletal rearrangement to afford unique pi-conjugated products: a thiopyrrolo-pentaphyrin embedded with a pyrrolo[1,2]isothiazole (2), a sulfur-free pentaphyrin incorporating an indolizine moiety (3), and a thiopyranyltriphyrinoid containing a 2H-thiopyran unit (4). Furthermore, 2 underwent desulfurization reactions to afford a fused pentaphyrin containing a pyrrolizine moiety (5) under mild conditions. Using expanded porphyrin scaffolds, oxidative thiophene cleavage and desulfurization of the hitherto unknown N-confused core-modified macrocycles would be a practical approach for developing unique polypyrrolic aromatic macrocycles.