A Palladium Complex as an Asymmetric π-Lewis Base Catalyst for Activating 1,3-Dienes
Here we report that palladium(0) complexes can coordinate in a η2 fashion to 1,3-dienes and significantly raise the energy of their highest occupied molecular orbital (HOMO) by donating the electrons from the d-orbitals to the empty antibonding molecular orbitals of double bonds (π*) via back-bonding. Thus, the uncoordinated double bond, as a more reactive partner on the basis of the principle of vinylogy, can directly attack imines, furnishing a formal hydrodienylation reaction enantioselectively. A chemoselective cascade vinylogous addition/allylic alkylation difunctionalization process between 1,3-dienes and imines with a nucleophilic group is also compatible, by trapping in situ formed π-allylpalladium species after initial ene addition. This π-Lewis base catalytic mode, featuring simple η2coordination, vinylogous activation, and compatibility with both conjugated neutral polyenes and electron-deficient polyenes, is elucidated by control experiments and density functional theory (DFT) calculations.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:143 |
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| Enthalten in: |
Journal of the American Chemical Society - 143(2021), 12 vom: 31. März, Seite 4809-4816 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Xiao, Ben-Xian [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 18.08.2021 Date Revised 18.08.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.1c01420 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM322874505 |
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| 245 | 1 | 2 | |a A Palladium Complex as an Asymmetric π-Lewis Base Catalyst for Activating 1,3-Dienes |
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| 500 | |a Date Revised 18.08.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Here we report that palladium(0) complexes can coordinate in a η2 fashion to 1,3-dienes and significantly raise the energy of their highest occupied molecular orbital (HOMO) by donating the electrons from the d-orbitals to the empty antibonding molecular orbitals of double bonds (π*) via back-bonding. Thus, the uncoordinated double bond, as a more reactive partner on the basis of the principle of vinylogy, can directly attack imines, furnishing a formal hydrodienylation reaction enantioselectively. A chemoselective cascade vinylogous addition/allylic alkylation difunctionalization process between 1,3-dienes and imines with a nucleophilic group is also compatible, by trapping in situ formed π-allylpalladium species after initial ene addition. This π-Lewis base catalytic mode, featuring simple η2coordination, vinylogous activation, and compatibility with both conjugated neutral polyenes and electron-deficient polyenes, is elucidated by control experiments and density functional theory (DFT) calculations | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 700 | 1 | |a Jiang, Bo |e verfasserin |4 aut | |
| 700 | 1 | |a Yan, Ru-Jie |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Jian-Xiang |e verfasserin |4 aut | |
| 700 | 1 | |a Xie, Ke |e verfasserin |4 aut | |
| 700 | 1 | |a Gao, Xin-Yue |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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