Diamine Synthesis via the Nitrogen-Directed Azidation of σ- and π-C-C Bonds
Diamines are essential building blocks for the synthesis of agrochemicals, drugs, and organic materials, yet their synthesis remains challenging, as both nitrogens need to be differentiated and diverse substitution patterns (1,2, 1,3, or 1,4) are required. We report herein a new strategy giving access to 1,2, 1,3, and 1,4 amido azides as orthogonally protected diamines based on the nitrogen-directed diazidation of alkenes, cyclopropanes, and cyclobutanes. Commercially available copper thiophene-2-carboxylate (CuTc, 2 mol %) as catalyst promoted the diazidation of both π and σ C-C bonds within 10 min in the presence of readily available oxidants and trimethylsilyl azide. Selective substitution of the formed α-amino azide by carbon nucleophiles (electron-rich aromatic, malonate, organosilicon, organoboron, organozinc, and organomagnesium compounds) was then achieved in a one-pot fashion, leading to the formation of 1,2-, 1,3-, and 1,4-diamines with the amino groups protected orthogonally as an amide/carbamate and an azide.
| 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), 31 vom: 11. Aug., Seite 11969-11975 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Wang, Ming-Ming [VerfasserIn] |
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| Anmerkungen: |
Date Completed 09.12.2021 Date Revised 14.12.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.1c06700 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM328837342 |
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| 245 | 1 | 0 | |a Diamine Synthesis via the Nitrogen-Directed Azidation of σ- and π-C-C Bonds |
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| 500 | |a Date Revised 14.12.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Diamines are essential building blocks for the synthesis of agrochemicals, drugs, and organic materials, yet their synthesis remains challenging, as both nitrogens need to be differentiated and diverse substitution patterns (1,2, 1,3, or 1,4) are required. We report herein a new strategy giving access to 1,2, 1,3, and 1,4 amido azides as orthogonally protected diamines based on the nitrogen-directed diazidation of alkenes, cyclopropanes, and cyclobutanes. Commercially available copper thiophene-2-carboxylate (CuTc, 2 mol %) as catalyst promoted the diazidation of both π and σ C-C bonds within 10 min in the presence of readily available oxidants and trimethylsilyl azide. Selective substitution of the formed α-amino azide by carbon nucleophiles (electron-rich aromatic, malonate, organosilicon, organoboron, organozinc, and organomagnesium compounds) was then achieved in a one-pot fashion, leading to the formation of 1,2-, 1,3-, and 1,4-diamines with the amino groups protected orthogonally as an amide/carbamate and an azide | ||
| 650 | 4 | |a Journal Article | |
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| 700 | 1 | |a Nguyen, Tin V T |e verfasserin |4 aut | |
| 700 | 1 | |a Waser, Jerome |e verfasserin |4 aut | |
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