Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer

Hall, Melissa N.; Lee, Maizie; Root, Thatcher W.; Davies, Huw M. L.; Stahl, Shannon S.

doi:10.1021/jacs.4c04430

Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer

Journal Article · Wed May 08 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c04430· OSTI ID:2429384

^[1]; Lee, Maizie ^[2]; ^[3]; ^[2]; ^[3]

University of Wisconsin, Madison, WI (United States); University of Wisconsin - Madison
Emory University, Atlanta, GA (United States)
University of Wisconsin, Madison, WI (United States)

Organic diazo compounds are versatile reagents in chemical synthesis and would benefit from improved synthetic accessibility, especially for larger scale applications. Here, we report a mild method for the synthesis of diazo compounds from hydrazones using a heterogeneous Fe-N-C catalyst, which has Fe ions dispersed within a graphitic nitrogen-doped carbon support. The reactions proceed readily at room temperature using O₂ (1 atm) as the oxidant. Aryl diazoesters, ketones, and amides are accessible, in addition to less stable diaryl diazo compounds. Initial-rate data show that the Fe-N-C catalyst achieves faster rates than a heterogeneous Pt/C catalyst. The oxidative dehydrogenation of hydrazones may be performed in tandem with Rh-catalyzed enantioselective C–H insertion and cyclopropanation of alkenes, without requiring isolation of the diazo intermediate. Furthermore, this sequence is showcased by using a flow reactor for continuous synthesis of diazo compounds.

View Accepted Manuscript (DOE)

Research Organization:: University of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 2429384

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer

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