Meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching

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

doi:10.1021/jacs.8b07973

Meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

39 Citations (Scopus)

Abstract

All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF ₂ -complex 3 was smoothly synthesized by 2-fold S _N Ar 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 ₄ 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?-congener 4 via oxidation with MnO ₂ and reduction with NaBH ₄ . Treatment of 3 or 4 with CuCl ₂ in the presence of NaOAc gave hetero bimetal complex 8.

Original language	English
Pages (from-to)	16553-16559
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	140
Issue number	48
DOIs	https://doi.org/10.1021/jacs.8b07973
Publication status	Published - 2018 Dec 5

Bibliographical note

Funding Information:
The work is supported by the National Nature Science Foundation of China (Grant Nos. 21772036, 21602058, and 21705055), Science and Technology Planning Project of Hunan Province (2018TP1017), and Scientific Research Fund of Hunan Provincial Education Department (Grant No. 16A125). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A020501 83). We thank Dr. Zier Yan (Rigaku Beijing corporation, China) for help in crystal analysis. We also thank Mr. Kyosuke Saito and Ko Furukawa for ESR measurements.

Publisher Copyright:
© 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.8b07973

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title = "Meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching",

abstract = " All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF 2 -complex 3 was smoothly synthesized by 2-fold S N Ar 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 4 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?-congener 4 via oxidation with MnO 2 and reduction with NaBH 4 . Treatment of 3 or 4 with CuCl 2 in the presence of NaOAc gave hetero bimetal complex 8.",

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

note = "Funding Information: The work is supported by the National Nature Science Foundation of China (Grant Nos. 21772036, 21602058, and 21705055), Science and Technology Planning Project of Hunan Province (2018TP1017), and Scientific Research Fund of Hunan Provincial Education Department (Grant No. 16A125). The work at Yonsei was supported by the Global Research Laboratory (GRL) Program funded by the Ministry of Science, ICT & Future, Korea (2013K1A1A2A020501 83). We thank Dr. Zier Yan (Rigaku Beijing corporation, China) for help in crystal analysis. We also thank Mr. Kyosuke Saito and Ko Furukawa for ESR measurements. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = dec,

day = "5",

doi = "10.1021/jacs.8b07973",

language = "English",

volume = "140",

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T1 - Meso-Triaryl-Substituted Smaragdyrins

T2 - Facile Aromaticity Switching

AU - Xie, Daguan

AU - Liu, Yang

AU - Rao, Yutao

AU - Kim, Gakhyun

AU - Zhou, Mingbo

AU - Yu, Donghai

AU - Xu, Ling

AU - Yin, Bangshao

AU - Liu, Shubin

AU - Tanaka, Takayuki

AU - Aratani, Naoki

AU - Osuka, Atsuhiro

AU - Liu, Qingyun

AU - Kim, Dongho

AU - Song, Jianxin

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PY - 2018/12/5

Y1 - 2018/12/5

N2 - All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF 2 -complex 3 was smoothly synthesized by 2-fold S N Ar 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 4 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?-congener 4 via oxidation with MnO 2 and reduction with NaBH 4 . Treatment of 3 or 4 with CuCl 2 in the presence of NaOAc gave hetero bimetal complex 8.

AB - All-aza smaragdyrin, a historic but elusive pentapyrrolic macrocycle, was successfully synthesized and characterized for the first time. [22]Smaragdyrin BF 2 -complex 3 was smoothly synthesized by 2-fold S N Ar 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 4 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?-congener 4 via oxidation with MnO 2 and reduction with NaBH 4 . Treatment of 3 or 4 with CuCl 2 in the presence of NaOAc gave hetero bimetal complex 8.

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ER -

Meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching

Abstract

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