Expansion of Azulenes as Nonbenzenoid Aromatic Compounds for C–H Activation: Rhodium- and Iridium-Catalyzed Oxidative Cyclization of Azulene Carboxylic Acids with Alkynes for the Synthesis of Azulenolactones and Benzoazulenes
| Autor: | Kyungsup Lee, Chanyoung Maeng, Seung Cheol Lee, Phil Ho Lee, Kyusik Um, Gi Hoon Ko, Yonghyeon Baek, Kooyeon Lee, Jeong-Yu Son, Gi Uk Han, Sang Hoon Han |
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| Rok vydání: | 2020 |
| Předmět: | |
| Zdroj: | The Journal of Organic Chemistry. 85:3824-3837 |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | Rhodium-catalyzed oxidative [4 + 2] cyclization reactions through the C-H activation of azulene carboxylic acids as nonbenzenoid aromatic compounds with symmetrical and unsymmetrical alkynes were developed under aerobic conditions, which produced azulenolactone derivatives with a wide substrate scope and excellent functional group tolerance. Interestingly, azulenic acids in reaction with alkynes underwent iridium-catalyzed [2 + 2 + 2] cyclization accompanied by decarboxylation to afford tetra(aryl)-substituted benzoazulene derivatives. The reactivity order for C-H activation reaction is greater toward azulene-6-carboxylic acid, azulene-1-carboxylic acid, and azulene-2-carboxylic acid. For the first time, the expansion of azulenes having directing group as nonbenzenoid aromatic compounds for C-H activation was successful, indicating that nonbenzenoid aromatic compounds can be used as good substrates for the C-H activation reaction. Therefore, the research area of C-H activation will certainly expand to nonbenzenoid aromatic compounds in future. |
| Databáze: | OpenAIRE |
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