Rational Synthesis of 5,10-Diazaporphyrins via Nucleophilic Substitution Reactions of α,α′-Dibromotripyrrin and Dihydrogenation to Give 5,10-Diazachlorins

Masataka Umetani, Gakhyun Kim, Takayuki Tanaka, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

Abstract

We report here the first rational synthesis of 5,10-diazaporphyrins via nucleophilic substitution reactions of α,α′-dibromotripyrrin. Uses of 1,3-diiminoisoindoline and 3,4-di(ethylsulfanyl)pyrrole-2,5-diimine as nucleophiles allowed for synthesis of 5,10-diazabenzoporphyrin (2) and 5,10-diaza-7,8-di(ethylsulfanyl)porphyrin (3). 3 was reduced to 5,10-diazaporphyrin (4), 5,10-diaza-2,3-dihydrogenated porphyrin (5), and 5,10-diaza-7,8-dihydrogenated porphyrin (6) with yields that were dependent upon reduction conditions. All the structures of these products were confirmed by X-ray crystallographic analysis. Their optical and electrochemical properties have been comparatively studied with those of 5,15-diazaporphyrin (7) and 5,15-diazachlorin (8). Furthermore, NH tautomers of 2 and 4 were observed as different species in solution, and the dynamic NH tautomeric behavior was studied in 4.

Original languageEnglish
Pages (from-to)3849-3857
Number of pages9
JournalJournal of Organic Chemistry
Volume85
Issue number5
DOIs
Publication statusPublished - 2020 Mar 6

Bibliographical note

Funding Information:
This work was supported by JSPS KAKENHI grant numbers (JP18K14199, JP16H00909, and JP18H03910). M.U. acknowledges a JSPS Fellowship for Young Scientists. T.T. thanks financial supports from Murata Science Foundation and Izumi Science and Technology Foundation. The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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