Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents
Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- and stereoselectively, and the resultant palladium(II) species undergo a cascade Suzuki reaction with organoboronic reagents. The substrate scope is substantial for the asymmetric three-component process, and the enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in a modular and cis-difunctionalized manner. Control experiments and density functional theory (DFT) calculations support the idea that the palladium(0) acts as a π-Lewis base catalyst by chemoselectively forming η2-complexes with the alkene moiety of 1,3-enynes, thus increasing the nucleophilicity of the alkyne group based on the principle of vinylogy, to attack imines enantioselectively. The preferable formation of aza-palladacyclopentene intermediates, via a 90° single bond rotation from the resultant π-allyl complex, guarantees the formal cis-carbopalladation of alkyne group. In addition, a palladium(0)-catalyzed enantioselective reductive coupling of 1,3-enyne and imine is realized by using formic acid as hydrogen transfer reagent.
| 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), 43 vom: 03. Nov., Seite 17989-17994 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
He, Qing [VerfasserIn] |
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| Links: |
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| Themen: |
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| Anmerkungen: |
Date Completed 03.02.2022 Date Revised 03.02.2022 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.1c09877 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM332096378 |
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| 245 | 1 | 0 | |a Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents |
| 264 | 1 | |c 2021 | |
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| 500 | |a Date Revised 03.02.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- and stereoselectively, and the resultant palladium(II) species undergo a cascade Suzuki reaction with organoboronic reagents. The substrate scope is substantial for the asymmetric three-component process, and the enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in a modular and cis-difunctionalized manner. Control experiments and density functional theory (DFT) calculations support the idea that the palladium(0) acts as a π-Lewis base catalyst by chemoselectively forming η2-complexes with the alkene moiety of 1,3-enynes, thus increasing the nucleophilicity of the alkyne group based on the principle of vinylogy, to attack imines enantioselectively. The preferable formation of aza-palladacyclopentene intermediates, via a 90° single bond rotation from the resultant π-allyl complex, guarantees the formal cis-carbopalladation of alkyne group. In addition, a palladium(0)-catalyzed enantioselective reductive coupling of 1,3-enyne and imine is realized by using formic acid as hydrogen transfer reagent | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 700 | 1 | |a Zhu, Lei |e verfasserin |4 aut | |
| 700 | 1 | |a Yang, Zhen-Hong |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Bo |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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