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The stereoselective synthesis of cis- and trans-fused pyrrolidine containing bicyclic azepine and oxepine derivatives using aza-Cope rearrangement-Mannich cyclization as a key stepстатья
- Авторы: Lukyanenko Evgeny, Belov Grigory M., Novoselov Anton M., Nechaev Mikhail, Kurkin Alexander V.
- Журнал: New Journal of Chemistry
- Год издания: 2022
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- DOI: 10.1039/D2NJ03936B
- Аннотация: The development of novel methods and strategies for the formation of fused five-, six-, and seven-membered ring structures is of utmost importance in organic syntheses. The present study describes the investigation of [3,3]-sigmatropic rearrangement to construct new cis- and trans-fused heterocyclic compounds, such as decahydropyrrolo[2,3-c]azepines, octahydro-1H-oxepino[4,5-b]pyrroles, and decahydropyrrolo[2,3-d]azepines, using the aza-Cope-Mannich reaction. Investigation of the [3,3]-sigmatropic rearrangement of 3-amino-4-vinyltetrahydro-2H-pyran-4-ol, 3-amino-4-vinylpiperidin-4-ol, and 4-amino-3-vinylpiperidin-3-ol derivatives revealed that the process proceeded with a high yield and diastereoselectivity. The stereoselectivity of the annulation process can be rationalized by examining the low-energy conformations of the trans-amino alcohol starting materials. These results demonstrate the efficiency and the potential of the the aza-Cope-Mannich reaction in the creation of cis- and trans-fused pyrrolidine containing bicyclic azepine and oxepine derivatives (5,7-bicyclic ring systems). The absolute configuration of the corresponding 5,7-bicyclic ketones was also established, which has rarely been achieved. The target scaffolds were achieved in 6-7 steps from commercially available starting materials and could be obtained in racemic form on a multigram scale.
- Добавил в систему: Куркин Александр Витальевич