Silver-catalyzed direct conversion of epoxides into cyclopropanes using N-triftosylhydrazones
© 2024. The Author(s)..
Epoxides, as a prominent small ring O-heterocyclic and the privileged pharmacophores for medicinal chemistry, have recently represented an ideal substrate for the development of single-atom replacements. The previous O-to-C replacement strategy for epoxides to date typically requires high temperatures to achieve low yields and lacks substrate range and functional group tolerance, so achieving this oxygen-carbon exchange remains a formidable challenge. Here, we report a silver-catalyzed direct conversion of epoxides into trifluoromethylcyclopropanes in a single step using trifluoromethyl N-triftosylhydrazones as carbene precursors, thereby achieving oxygen-carbon exchange via a tandem deoxygenation/[2 + 1] cycloaddition. The reaction shows broad tolerance of functional groups, allowing routine cheletropic olefin synthesis in a strategy for the net oxygen-carbon exchange reaction. The utility of this method is further showcased with the late-stage diversification of epoxides derived from bioactive natural products and drugs. Mechanistic experiments and DFT calculations elucidate the reaction mechanism and the origin of the chemo- and stereoselectivity.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:15 |
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| Enthalten in: |
Nature communications - 15(2024), 1 vom: 02. März, Seite 1951 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Li, Linxuan [VerfasserIn] |
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Date Revised 06.03.2024 published: Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1038/s41467-024-46188-w |
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| Förderinstitution / Projekttitel: |
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| 520 | |a © 2024. The Author(s). | ||
| 520 | |a Epoxides, as a prominent small ring O-heterocyclic and the privileged pharmacophores for medicinal chemistry, have recently represented an ideal substrate for the development of single-atom replacements. The previous O-to-C replacement strategy for epoxides to date typically requires high temperatures to achieve low yields and lacks substrate range and functional group tolerance, so achieving this oxygen-carbon exchange remains a formidable challenge. Here, we report a silver-catalyzed direct conversion of epoxides into trifluoromethylcyclopropanes in a single step using trifluoromethyl N-triftosylhydrazones as carbene precursors, thereby achieving oxygen-carbon exchange via a tandem deoxygenation/[2 + 1] cycloaddition. The reaction shows broad tolerance of functional groups, allowing routine cheletropic olefin synthesis in a strategy for the net oxygen-carbon exchange reaction. The utility of this method is further showcased with the late-stage diversification of epoxides derived from bioactive natural products and drugs. Mechanistic experiments and DFT calculations elucidate the reaction mechanism and the origin of the chemo- and stereoselectivity | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Sivaguru, Paramasivam |e verfasserin |4 aut | |
| 700 | 1 | |a Wei, Dandan |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Menglin |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Qingwen |e verfasserin |4 aut | |
| 700 | 1 | |a Dong, Shuai |e verfasserin |4 aut | |
| 700 | 1 | |a Casali, Emanuele |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Nan |e verfasserin |4 aut | |
| 700 | 1 | |a Zanoni, Giuseppe |e verfasserin |4 aut | |
| 700 | 1 | |a Bi, Xihe |e verfasserin |4 aut | |
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