Abstract
Double ring expansion from a 5,15-diarylporphyrin to a 5,16-diaryl-10,11,21,22-tetradehydro[20]porphyrin(2.1.2.1) occurred through a reaction sequence consisting of oxidation with PbO2to 5,15-dioxoporphodimethene, a Corey–Fuchs reaction with tetrabromomethane in the presence of triphenylphosphine, and Fritsch–Buttenberg–Wiechell rearrangement triggered by tert-butyllithium. The obtained tetradehydro[20]porphyrin(2.1.2.1) and its mono- and dihydrogenated congeners exhibited 20 π antiaromatic character, whereas overhydrogenated congeners bearing a saturated bridge were nonaromatic owing to disrupted π conjugation.
| Original language | English |
|---|---|
| Pages (from-to) | 8095-8099 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 55 |
| Issue number | 28 |
| DOIs | |
| Publication status | Published - 2016 Jul 4 |
All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
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Umetani, M., Tanaka, T., Kim, T., Kim, D., & Osuka, A. (2016). Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1). Angewandte Chemie - International Edition, 55(28), 8095-8099. https://doi.org/10.1002/anie.201602874