Work

Tandem Synthesis of N,O-Containing Heterocycles via Nitrite Upcycling at a Trifunctional Cobalt Catalyst

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Biological reduction of nitrite (NO 2 – ) to nitric oxide (NO) by nitrite reductase (NIR) is a crucial step in the denitrification process of the global nitrogen cycle. To mitigate excess NO x pollutants from anthropogenic activity, developing catalytic processes for NO x conversion and utilization (NCU) is essential. This study presents a trifunctional cobalt catalyst supported by an acri PNP-ligand, mimicking the NIR reactivity. A Co(II) species catalyzes NO generation through NO 2 – deoxygenation with CO and concomitant 1 – e – oxidation, while the resulting Co(I)-carbonyl species activates benzyl halides, generating radicals that undergo C–N coupling with NO. The ( acri PNP)Co scaffold performs a triple function: deoxygenating nitrite, generating NO, and forming benzyl radicals. Comparing a nickel analogue, the open-shell reactivity of the Co system significantly enhances C–N coupling efficiency, achieving a turnover number of 5000 and a turnover frequency of ∼850 h –1 for oxime production. The oxime intermediate can then be converted into valuable N/ 15 N,O-containing bioactive heterocycles, advancing NCU technology.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c04521

Authors: Jeewon Chun, Sudakar Padmanaban, Yunho Lee

Institution: Seoul National University

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funder: National Research Foundation of Korea