meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching

被引：54

作者：

Xie, Daguan ^{[1
]}

Liu, Yang ^{[1
]}

Rao, Yutao ^{[1
]}

Kim, Gakhyun ^{[4
,5
]}

Zhou, Mingbo ^{[1
]}

Yu, Donghai ^{[1
]}

Xu, Ling ^{[1
]}

Yin, Bangshao ^{[1
]}

Liu, Shubin ^{[1
,6
]}

Tanaka, Takayuki ^{[2
]}

Aratani, Naoki ^{[3
]}

Osuka, Atsuhiro ^{[1
,2
]}

Liu, Qingyun ^{[7
]}

Kim, Dongho ^{[4
,5
]}

Song, Jianxin ^{[1
]}

机构：

[1] Hunan Normal Univ, Key Lab Chem Biol & Tradit Chinese Med, Minist Educ China, Key Lab Assembly & Applicat Organ Funct Mol Hunan, Changsha 410081, Hunan, Peoples R China

[2] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan

[3] Nara Inst Sci & Technol, Takayama, Ikoma 6300192, Japan

[4] Yonsei Univ, Spect Lab Funct Elect Syst, Seoul 03722, South Korea

[5] Yonsei Univ, Dept Chem, Seoul 03722, South Korea

[6] Univ N Carolina, Informat Technol Serv, Div Res Comp, Chapel Hill, NC 27599 USA

[7] Shandong Univ Sci & Technol, Coll Chem & Environm Engn, Qingdao 266510, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 48期

关键词：

INDEPENDENT CHEMICAL-SHIFTS; EXPANDED PORPHYRINS;

D O I：

10.1021/jacs.8b07973

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF2-complex 3 was smoothly synthesized by 2-fold SNAr 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 NaBH4 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 20 pi-congener 4 via oxidation with MnO2 and reduction with NaBH4. Treatment of 3 or 4 with CuCl2 in the presence of NaOAc gave hetero bimetal complex 8.

引用

页码：16553 / 16559

页数：7

共 32 条

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