Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 62, Issue 1, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202212174
Keywords
Antiaromaticity; N-Confused Porphyrin; Porphyrinoids; Sapphyrin; Skeletal Rearrangement
Categories
Funding
- Shanghai Municipal Science and Technology Major Project [2018SHZDZX03]
- International Cooperation Program of Shanghai Science and Technology Committee [17520750100]
- NSFC [22131005, 21971063, 22201074, 22075077]
- Program of Introducing Talents of Discipline to Universities [B160170]
- Fundamental Research Funds for the Central Universities [222201717003]
- Program of Shanghai Academic Research Leader [20XD1401400]
- JST PREST [JPMJPR2103]
- Japan Society for the Promotion of Science (JSPS) [JP20H00406, JP21 K18984]
- Swedish Research Council [2018-05973, 2020-04600]
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In this study, we report the synthesis of a 20 pi antiaromatic sapphyrin isomer, which exhibits a reactivity for further oxidation due to its distinct antiaromatic electronic structure. The resulting compound possesses a unique spiro-carbon-containing [5.6.5.6]-tetracyclic structure and can be easily transformed to novel porphyrinoids with variable aromaticity. This research highlights the synthesis of porphyrinoid compounds with different aromatic properties.
Sapphyrin is a pentapyrrolic expanded porphyrin with a 22 pi aromatic character. Herein, we report the synthesis of a 20 pi antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P-5 with a terminal beta-linked pyrrole. The resulting isomer 1, containing a mis-linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro-carbon-containing [5.6.5.6]-tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone-appended N-confused corrole 3, and thermal fusion gave a [5.6.5.7]-tetracyclic-ring-embedded 14 pi aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis-linked pyrrole moiety of P-5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity.
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