Revisiting Arene C(sp2 )−H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway
| Autor: | Yoonsu Park, Sukbok Chang, Dong-Wook Kim, Yeong Bum Kim, Yeongyu Hwang |
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| Rok vydání: | 2018 |
| Předmět: |
Reaction mechanism
010405 organic chemistry chemistry.chemical_element General Chemistry General Medicine Electrophilic aromatic substitution 010402 general chemistry Combinatorial chemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry Intramolecular force Iridium Computational analysis Amination |
| Zdroj: | Angewandte Chemie. 130:13753-13757 |
| ISSN: | 0044-8249 |
| Popis: | Two mechanistic pathways, that is, electrocyclization and electrophilic aromatic substitution, are operative in most intramolecular C-H amination reactions proceeding by metal nitrenoid catalysis. Reported here is an alternative mechanistic scaffold leading to benzofused δ-lactams selectively. Integrated experimental and computational analysis revealed that the reaction proceeds by a key spirocyclization step followed by a skeletal rearrangement. Based on this mechanistic insight, a new synthetic route to spirolactams has been developed. |
| Databáze: | OpenAIRE |
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