Enantioselective Synthesis of Quaternary Oxindoles : Desymmetrizing Staudinger-Aza-Wittig Reaction Enabled by a Bespoke HypPhos Oxide Catalyst
This paper describes a catalytic asymmetric Staudinger-aza-Wittig reaction of (o-azidoaryl)malonates, allowing access to chiral quaternary oxindoles through phosphine oxide catalysis. We designed a novel HypPhos oxide catalyst to enable the desymmetrizing Staudinger-aza-Wittig reaction through the PIII/PV═O redox cycle in the presence of a silane reductant and an IrI-based Lewis acid. The reaction occurs under mild conditions, with good functional group tolerance, a wide substrate scope, and excellent enantioselectivity. Density functional theory revealed that the enantioselectivity in the desymmetrizing reaction arose from the cooperative effects of the IrI species and the HypPhos catalyst. The utility of this methodology is demonstrated by the (formal) syntheses of seven alkaloid targets: (-)-gliocladin C, (-)-coerulescine, (-)-horsfiline, (+)-deoxyeseroline, (+)-esermethole, (+)-physostigmine, and (+)-physovenine.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2022 |
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| Erschienen: |
2022 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:144 |
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| Enthalten in: |
Journal of the American Chemical Society - 144(2022), 46 vom: 23. Nov., Seite 21318-21327 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Xie, Changmin [VerfasserIn] |
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| Links: |
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| Themen: |
Alkaloids |
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| Anmerkungen: |
Date Completed 24.11.2022 Date Revised 24.12.2023 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.2c09421 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM348886411 |
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| 245 | 1 | 0 | |a Enantioselective Synthesis of Quaternary Oxindoles |b Desymmetrizing Staudinger-Aza-Wittig Reaction Enabled by a Bespoke HypPhos Oxide Catalyst |
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| 500 | |a Date Completed 24.11.2022 | ||
| 500 | |a Date Revised 24.12.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a This paper describes a catalytic asymmetric Staudinger-aza-Wittig reaction of (o-azidoaryl)malonates, allowing access to chiral quaternary oxindoles through phosphine oxide catalysis. We designed a novel HypPhos oxide catalyst to enable the desymmetrizing Staudinger-aza-Wittig reaction through the PIII/PV═O redox cycle in the presence of a silane reductant and an IrI-based Lewis acid. The reaction occurs under mild conditions, with good functional group tolerance, a wide substrate scope, and excellent enantioselectivity. Density functional theory revealed that the enantioselectivity in the desymmetrizing reaction arose from the cooperative effects of the IrI species and the HypPhos catalyst. The utility of this methodology is demonstrated by the (formal) syntheses of seven alkaloid targets: (-)-gliocladin C, (-)-coerulescine, (-)-horsfiline, (+)-deoxyeseroline, (+)-esermethole, (+)-physostigmine, and (+)-physovenine | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 4 | |a Research Support, N.I.H., Extramural | |
| 650 | 7 | |a Oxindoles |2 NLM | |
| 650 | 7 | |a Oxides |2 NLM | |
| 650 | 7 | |a Alkaloids |2 NLM | |
| 700 | 1 | |a Kim, Jacob |e verfasserin |4 aut | |
| 700 | 1 | |a Mai, Binh Khanh |e verfasserin |4 aut | |
| 700 | 1 | |a Cao, Shixuan |e verfasserin |4 aut | |
| 700 | 1 | |a Ye, Rong |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Xin-Yi |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Peng |e verfasserin |4 aut | |
| 700 | 1 | |a Kwon, Ohyun |e verfasserin |4 aut | |
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