Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis
Carboxylic acids are not readily applied as carbon-based nucleophiles due to their intrinsic acidic group. Here, we demonstrate that free (E,E)-2,4-dienoic acids form electron-neutral and highest occupied molecular orbital-raised η2-complexes with Pd(0) and undergo Friedel-Crafts-type additions to imines with exclusive α-regioselectivity, giving formal dienylated products after decarboxylation. Unusual and switchable (E,E)- and (Z,E)-selectivity, along with excellent enantioselectivity, is achieved via ligand-controlled outer-sphere or inner-sphere reaction modes, respectively, which are well supported by comprehensive density functional theory calculation studies. An unprecedented formal reductive Mannich reaction between (E,E)-dienoic acids and imines is also developed to furnish enantioenriched β-amino acid derivatives.
| 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), 49 vom: 14. Dez., Seite 22689-22697 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Tan, Shun-Zhong [VerfasserIn] |
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| Links: |
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| Themen: |
5TWQ1V240M |
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| Anmerkungen: |
Date Completed 15.12.2022 Date Revised 22.12.2022 published: Print-Electronic Citation Status MEDLINE |
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| doi: |
10.1021/jacs.2c10004 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM349813604 |
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| 245 | 1 | 0 | |a Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis |
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| 500 | |a Date Revised 22.12.2022 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status MEDLINE | ||
| 520 | |a Carboxylic acids are not readily applied as carbon-based nucleophiles due to their intrinsic acidic group. Here, we demonstrate that free (E,E)-2,4-dienoic acids form electron-neutral and highest occupied molecular orbital-raised η2-complexes with Pd(0) and undergo Friedel-Crafts-type additions to imines with exclusive α-regioselectivity, giving formal dienylated products after decarboxylation. Unusual and switchable (E,E)- and (Z,E)-selectivity, along with excellent enantioselectivity, is achieved via ligand-controlled outer-sphere or inner-sphere reaction modes, respectively, which are well supported by comprehensive density functional theory calculation studies. An unprecedented formal reductive Mannich reaction between (E,E)-dienoic acids and imines is also developed to furnish enantioenriched β-amino acid derivatives | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
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| 650 | 7 | |a Anions |2 NLM | |
| 700 | 1 | |a Chen, Peng |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Lei |e verfasserin |4 aut | |
| 700 | 1 | |a Gan, Meng-Qi |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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