Synthesis and Aromaticity of Benzene-Fused Doubly N-Confused Porphyrins

Hidemitsu Uno; Kota Muramatsu; Shogo Hiraoka; Hiroyuki Tahara; Mako Hirose; Eidai Tamura; Tatsumi Shiraishi; John Mack; Nagao Kobayashi; Shigeki Mori; Tetsuo Okujima; Masayoshi Takase

doi:10.1002/chem.202000339

Synthesis and Aromaticity of Benzene-Fused Doubly N-Confused Porphyrins

Chemistry. 2020 May 4;26(25):5701-5708. doi: 10.1002/chem.202000339. Epub 2020 Apr 20.

Authors

Affiliations

¹ Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama, 790-8577, Japan.
² Institute for Nanotechnology Innovation, Department of Chemistry, Rhodes University, Grahamstown, 6140, South Africa.
³ Faculty of Textile Science and Technology, Shinshu University, Ueda, 386-8567, Japan.
⁴ Advanced Research Support Center, Ehime University, Matsuyama, 790-8577, Japan.

PMID: 32147874
DOI: 10.1002/chem.202000339

Abstract

A bicyclo[2.2.2]octadiene(BCOD)-fused bis(dipyrromethane) derivative was reacted with methylal in the presence of trifluoroacetic acid followed by oxidation with chloranil to give a doubly N-confused phlorin derivative, which did not undergo the retro-Diels-Alder reaction extruding an ethylene molecule on heating. In contrast, a 7-tert-butoxybicyclo[2.2.1]heptadiene(7-BuOBCHD)-fused bis(dipyrromethane) yielded benzene-ring-fused doubly N-confused porphyrins by following similar reaction sequences.

Keywords: aromaticity; macrocycles; porphyrins; proton-deuteron exchange.

Grants and funding

19K05422/Japan Society for the Promotion of Science