Enantioselective Silver and Amine Co-catalyzed Desymmetrizing Cycloisomerization of Alkyne-Linked Cyclohexanones
| Autor: | Swarup Datta, Darren J. Dixon, Robert S. Paton, Rubén Manzano |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
Ketone Bicyclic molecule 010405 organic chemistry Enantioselective synthesis Alkyne General Chemistry General Medicine 010402 general chemistry Desymmetrization 01 natural sciences Catalysis Enamine 3. Good health 0104 chemical sciences chemistry.chemical_compound Cycloisomerization chemistry Organic chemistry Chirality (chemistry) |
| Zdroj: | Angewandte Chemie. 129:5928-5932 |
| ISSN: | 0044-8249 |
| DOI: | 10.1002/ange.201612048 |
| Popis: | A silver(I) and amine co-catalyzed desymmetrization of 4-propargylamino cyclohexanones for the direct enantioselective synthesis of 2-azabicyclo[3.3.1]nonanes is described. Exploiting reactivity arising from dual activation of the pendant terminal alkyne by silver(I) and the ketone moiety through transient enamine formation, this synthetically relevant transformation is easy to perform, efficient and broad in scope. High enantioselectivity (up to 96 % ee) was achieved by exploiting a significant matching effect between the chirality of a cinchona alkaloid-derived aminophosphine ligand for the silver(I) salt and the 2-bis(aryl)methylpyrrolidine catalyst which was rationalized by DFT calculations. This allowed for the preparation of both enantiomers of the bicyclic product with near-identical stereocontrol. |
| Databáze: | OpenAIRE |
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