中位三芳基取代的翠绿啉：简便的芳香性切换

meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching.

作者信息

Xie Daguan, Liu Yang, Rao Yutao, Kim Gakhyun, Zhou Mingbo, Yu Donghai, Xu Ling, Yin Bangshao, Liu Shubin, Tanaka Takayuki, Aratani Naoki, Osuka Atsuhiro, Liu Qingyun, Kim Dongho, Song Jianxin

机构信息

Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province , Hunan Normal University , Changsha 410081 , China.

Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry , Yonsei University , Seoul 03722 , Korea.

出版信息

J Am Chem Soc. 2018 Dec 5;140(48):16553-16559. doi: 10.1021/jacs.8b07973. Epub 2018 Nov 27.

DOI:10.1021/jacs.8b07973

PMID:30421611

Abstract

All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF-complex 3 was smoothly synthesized by 2-fold SAr reaction of 1,9-dibromo-5-mesityldipyrrin with 5,10-dimesityltripyrrane. Treatment of 3 with methanesulfonic acid gave [20]smaragdyrin 5 as a stable antiaromatic compound. Reduction of 5 with NaBH under inert conditions gave [22]smaragdyrin 6 as an aromatic congener, which was easily oxidized back to 5 in the air. Complex 3 was interconvertible with its 20π-congener 4 via oxidation with MnO and reduction with NaBH. Treatment of 3 or 4 with CuCl in the presence of NaOAc gave hetero bimetal complex 8.

摘要

全氮祖母绿卟啉，一种历史悠久但难以捉摸的五吡咯大环化合物，首次成功合成并得到表征。[22]祖母绿卟啉BF配合物3通过1,9 - 二溴 - 5 - 均三甲苯基二吡咯与5,10 - 二均三甲苯基三吡咯的两次亲核芳香取代反应顺利合成。用甲磺酸处理3得到[20]祖母绿卟啉5，它是一种稳定的反芳香族化合物。在惰性条件下用硼氢化钠还原5得到[22]祖母绿卟啉6，它是一种芳香族同系物，在空气中很容易被氧化回5。配合物3通过用二氧化锰氧化和用硼氢化钠还原可与其20π同系物4相互转化。在醋酸钠存在下用氯化铜处理3或4得到异双金属配合物8。