Iron‐Catalyzed Intermolecular C−H Amination Assisted by an Isolated Iron‐Imido Radical Intermediate

Zars, Ethan; Pick, Lisa; Swain, Abinash; Bhunia, Mrinal; Carroll, Patrick J.; Munz, Dominik; Meyer, Karsten; Mindiola, Daniel J.

doi:10.1002/anie.202311749

Iron‐Catalyzed Intermolecular C−H Amination Assisted by an Isolated Iron‐Imido Radical Intermediate

Journal Article · Tue Oct 10 00:00:00 EDT 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202311749· OSTI ID:2573751

Zars, Ethan ^[1]; Pick, Lisa ^[2]; Swain, Abinash ^[3]; Bhunia, Mrinal ^[1]; Carroll, Patrick J. ^[1]; Munz, Dominik ^[3]; Meyer, Karsten ^[2]; ^[1]

University of Pennsylvania, Philadelphia, PA (United States)
Friedrich-Alexander-Universität Erlangen (Germany)
Saarland University, Saarbrücken (Germany)

Here we report the use of a base metal complex [(^tBupyrpyrr₂)Fe(OEt₂)] (1-OEt₂) (^tBupyrpyrr₂²⁻=3,5-tBu₂-bis(pyrrolyl)pyridine) as a catalyst for intermolecular amination of C_sp3−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 [(^tBupyrpyrr₂)Fe{=N(2,6-Me₂-4-tBu-C₆H₂)] (1-imido) can be isolated in 56 % yield, and spectroscopic, magnetometric, and computational studies confirmed it to be an S = 1 Fe^IV complex. Complex 1-imido reacts with 2 a to produce the ferrous aniline adduct [(^tBupyrpyrr₂)Fe{NH(2,6-Me₂-4-tBu-C₆H₂)(C₁₄H₁₁)}] (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.

View Accepted Manuscript (DOE)

Research Organization:: University of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0023340

OSTI ID:: 2573751

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 51 Vol. 62; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Organorhenium imido complexes: Synthese, structure, and reactivity

Journal Article · Wed Jan 31 23:00:00 EST 1990 · Organometallics; (USA) · OSTI ID:7108165

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Iron‐Catalyzed Intermolecular C−H Amination Assisted by an Isolated Iron‐Imido Radical Intermediate

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