| Autor: |
Stephen M. Bierschenk, Judy Y. Pan, Nicholas S. Settineri, Ulrike Warzok, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste |
| Rok vydání: |
2022 |
| Předmět: |
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| Zdroj: |
Journal of the American Chemical Society. 144(25) |
| ISSN: |
1520-5126 |
| Popis: |
A highly enantioselective aza-Darzens reaction (up to 99% ee) catalyzed by an enantiopure supramolecular host has been discovered. To understand the role of host structure on reaction outcome, nine new gallium(III)-based enantiopure supramolecular assemblies were prepared via substitution of the external chiral amide. Despite the distal nature of the substitution in these catalysts, changes in enantioselectivity (61 to 90% ee) in the aziridine product were observed. The enantioselectivities were correlated to the flexibility of the supramolecular host scaffold as measured by the kinetics of exchange of a model cationic guest. This correlation led to the development of a best-in-class catalyst by substituting the gallium(III)-based host with one based on indium(III), which generated the most flexible and selective catalyst. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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