Enantioselective Ir-Catalyzed Allyl Alkylation/Semipinacol Rearrangement
The semipinacol rearrangement is a powerful and versatile method for constructing all-carbon quaternary stereocenters. The development of catalytic asymmetric semipinacol rearrangements using multifunctionalizable electrophiles remains highly sought-after in organic synthesis. In this study, a catalytic enantioselective allylic cation-induced semipinacol rearrangement reaction was presented that enables the simultaneous construction of two skipped chiral carbon centers. Chiral Ir(I)-(P,olefin) and Sc(OTf)3 catalysts cooperatively initiate the asymmetric allylic alkylation of alkenyl cyclobutanols with allylic alcohols, triggering ring expansion of the cyclobutanol moiety through a stereoselective 1,2-alkyl migration. The reaction afforded a range of cyclopentanones bearing an α-quaternary carbon that is adjacent to a chiral allyl scaffold. The products were applied to synthesize enantioenriched fused tricyclopentanoids bearing four stereogenic carbon centers.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:26 |
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| Enthalten in: |
Organic letters - 26(2024), 6 vom: 16. Feb., Seite 1224-1228 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Zhao, Sumei [VerfasserIn] |
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| Anmerkungen: |
Date Revised 16.02.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.orglett.4c00025 |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM367951045 |
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| 520 | |a The semipinacol rearrangement is a powerful and versatile method for constructing all-carbon quaternary stereocenters. The development of catalytic asymmetric semipinacol rearrangements using multifunctionalizable electrophiles remains highly sought-after in organic synthesis. In this study, a catalytic enantioselective allylic cation-induced semipinacol rearrangement reaction was presented that enables the simultaneous construction of two skipped chiral carbon centers. Chiral Ir(I)-(P,olefin) and Sc(OTf)3 catalysts cooperatively initiate the asymmetric allylic alkylation of alkenyl cyclobutanols with allylic alcohols, triggering ring expansion of the cyclobutanol moiety through a stereoselective 1,2-alkyl migration. The reaction afforded a range of cyclopentanones bearing an α-quaternary carbon that is adjacent to a chiral allyl scaffold. The products were applied to synthesize enantioenriched fused tricyclopentanoids bearing four stereogenic carbon centers | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Yue, Wenxing |e verfasserin |4 aut | |
| 700 | 1 | |a Yang, Min |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Xuanfeng |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Bin |e verfasserin |4 aut | |
| 700 | 1 | |a Gao, Yuanji |e verfasserin |4 aut | |
| 700 | 1 | |a Yu, Wenhao |e verfasserin |4 aut | |
| 700 | 1 | |a Ni, Hai-Liang |e verfasserin |4 aut | |
| 700 | 1 | |a Hu, Ping |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Bi-Qin |e verfasserin |4 aut | |
| 700 | 1 | |a Cao, Peng |e verfasserin |4 aut | |
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