Judge, Neil; Hevia, Eva (2023). Alkali-Metal-Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis-Amide Zn(TMP)2. Angewandte Chemie. International edition, 62(29), e202303099. Wiley 10.1002/anie.202303099
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Angew_Chem_Int_Ed_-_2023_-_Judge_-_Alkali_Metal_Alkoxide_Powered_Zincation_of_Fluoroarenes_Employing_Zinc_Bis_Amide_Zn_TMP.pdf - Accepted Version Available under License Publisher holds Copyright. Download (4MB) | Preview |
Reminiscent of Lochmann-Schlosser superbase recipes, the addition of two molar equivalents of KOtBu to Zn(TMP)2(TMP = 2,2,6,6-tetramethylpiperidide) transforms this mild zinc bis-amide base to a powerful metalating agent able to perform facile regioselective zincation of a wide range of sensitive fluoroarenes. Structural authentication of the intermediates post Zn-H exchange demonstrates activation of both TMP groups to form a range of higher order bis-aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing the role of KOtBu reveal that the first equivalent undergoes co-complexation with Zn(TMP)2, enabling kinetic activation of the amide groups; whereas the second equivalent stabilizes the metalated intermediate preventing ligand redistribution. Showcasing its metalating power, this bimetallic KOtBu/Zn(TMP)2 partnership, can effect zincation of toluene and benzene at room temperature.
Item Type: |
Journal Article (Original Article) |
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Division/Institute: |
08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP) |
UniBE Contributor: |
Judge, Neil Ronald, Hevia Freire, Eva |
Subjects: |
500 Science > 570 Life sciences; biology 500 Science > 540 Chemistry |
ISSN: |
1521-3773 |
Publisher: |
Wiley |
Language: |
English |
Submitter: |
Pubmed Import |
Date Deposited: |
24 Mar 2023 14:03 |
Last Modified: |
25 Mar 2024 00:25 |
Publisher DOI: |
10.1002/anie.202303099 |
PubMed ID: |
36952317 |
Uncontrolled Keywords: |
Alkoxides cooperative effects fluoroarenes metalation zinc |
BORIS DOI: |
10.48350/180608 |
URI: |
https://boris.unibe.ch/id/eprint/180608 |
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