Asymmetric Formal Nucleophilic o-Cresolylation with Morita-Baylis-Hillman Carbonates of 2-Cyclohexenones via Palladium Catalysis
Here we report an asymmetric formal nucleophilic o-cresolylation reaction with the Morita-Baylis-Hillman (MBH) carbonates from 2-cyclohexanones and diverse aldehydes under palladium catalysis, by in situ generation of electron-neutral and HOMO-raised η2-Pd(0)-dienone complexes via an oxidative insertion/π-σ-isomerization/β-H elimination activation sequence. The subsequent umpolung vinylogous addition to a variety of imines is realized upon Pd(0)-mediated π-Lewis base catalysis, finally furnishing o-cresolylated products followed by another cascade of a π-σ-isomerization/β-H elimination/aromatization process. Moderate to excellent diastereo- and enantioselectivity are achieved for substantial substrate assemblies by employing a newly designed bulky chiral phosphonamidite ligand, and the resultant multifunctional products can be facilely elaborated to access diverse enantioenriched architectures. In addition, the catalytic reaction pathway is finely illuminated by control experiments.
| 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), 22 vom: 08. Juni, Seite 9564-9569 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Song, Xue [VerfasserIn] |
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| Links: |
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| Themen: |
2-cyclohexen-1-one |
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| Anmerkungen: |
Date Completed 09.06.2022 Date Revised 06.07.2022 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.2c04101 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM341453730 |
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| 500 | |a Date Revised 06.07.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Here we report an asymmetric formal nucleophilic o-cresolylation reaction with the Morita-Baylis-Hillman (MBH) carbonates from 2-cyclohexanones and diverse aldehydes under palladium catalysis, by in situ generation of electron-neutral and HOMO-raised η2-Pd(0)-dienone complexes via an oxidative insertion/π-σ-isomerization/β-H elimination activation sequence. The subsequent umpolung vinylogous addition to a variety of imines is realized upon Pd(0)-mediated π-Lewis base catalysis, finally furnishing o-cresolylated products followed by another cascade of a π-σ-isomerization/β-H elimination/aromatization process. Moderate to excellent diastereo- and enantioselectivity are achieved for substantial substrate assemblies by employing a newly designed bulky chiral phosphonamidite ligand, and the resultant multifunctional products can be facilely elaborated to access diverse enantioenriched architectures. In addition, the catalytic reaction pathway is finely illuminated by control experiments | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 650 | 7 | |a Carbonates |2 NLM | |
| 650 | 7 | |a Cyclohexanones |2 NLM | |
| 650 | 7 | |a 2-cyclohexen-1-one |2 NLM | |
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| 700 | 1 | |a Zhang, Jie |e verfasserin |4 aut | |
| 700 | 1 | |a Wu, Yu-Xing |e verfasserin |4 aut | |
| 700 | 1 | |a Ouyang, Qin |e verfasserin |4 aut | |
| 700 | 1 | |a Du, Wei |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Ying-Chun |e verfasserin |4 aut | |
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