Please use this identifier to cite or link to this item:
doi:10.22028/D291-41517
Title: | Iron-Catalyzed Intermolecular C−H Amination Assisted by an Isolated Iron-Imido Radical Intermediate |
Author(s): | Zars, Ethan Pick, Lisa Swain, Abinash Bhunia, Mrinal Carroll, Patrick J. Munz, Dominik Meyer, Karsten Mindiola, Daniel J. |
Language: | English |
Title: | Angewandte Chemie : International Edition |
Volume: | 62 |
Issue: | 51 |
Publisher/Platform: | Wiley |
Year of Publication: | 2023 |
Free key words: | Amination C−H Activation Imido Insertion Nitrene |
DDC notations: | 540 Chemistry |
Publikation type: | Journal Article |
Abstract: | Here we report the use of a base metal complex [(tBu pyrpyrr2 )Fe(OEt2 )] (1-OEt2 ) (tBu pyrpyrr2 2- =3,5-tBu2 -bis(pyrrolyl)pyridine) as a catalyst for intermolecular amination of Csp3 -H bonds of 9,10-dihydroanthracene (2 a) using 2,4,6-trimethyl phenyl azide (3 a) as the nitrene source. The reaction is complete within one hour at 80 °C using as low as 2 mol % 1-OEt2 with control in selectivity for single C-H amination versus double C-H amination. Catalytic C-H amination reactions can be extended to other substrates such as cyclohexadiene and xanthene derivatives and can tolerate a variety of aryl azides having methyl groups in both ortho positions. Under stoichiometric conditions the imido radical species [(tBu pyrpyrr2 )Fe{=N(2,6-Me2 -4-tBu-C6 H2 )] (1-imido) can be isolated in 56 % yield, and spectroscopic, magnetometric, and computational studies confirmed it to be an S = 1 FeIV complex. Complex 1-imido reacts with 2 a to produce the ferrous aniline adduct [(tBu pyrpyrr2 )Fe{NH(2,6-Me2 -4-tBu-C6 H2 )(C14 H11 )}] (1-aniline) in 45 % yield. Lastly, it was found that complexes 1-imido and 1-aniline are both competent intermediates in catalytic intermolecular C-H amination. |
DOI of the first publication: | 10.1002/anie.202311749 |
URL of the first publication: | https://onlinelibrary.wiley.com/doi/10.1002/anie.202311749 |
Link to this record: | urn:nbn:de:bsz:291--ds-415176 hdl:20.500.11880/37190 http://dx.doi.org/10.22028/D291-41517 |
ISSN: | 1521-3773 1433-7851 |
Date of registration: | 29-Jan-2024 |
Third-party funds sponsorship: | ERC |
Sponsorship ID: | 948185 |
EU-Projectnumber: | info:eu-repo/grantAgreement/EC/ERC/948185/EU//PUSH-IT |
Faculty: | NT - Naturwissenschaftlich- Technische Fakultät |
Department: | NT - Chemie |
Professorship: | NT - Prof. Dr. Dominik Munz |
Collections: | SciDok - Der Wissenschaftsserver der Universität des Saarlandes |
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Angew Chem Int Ed - 2023 - Zars - Iron‐Catalyzed Intermolecular C H Amination Assisted by an Isolated Iron‐Imido Radical.pdf | Manuskript | 1,62 MB | Adobe PDF | View/Open |
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