Direct synthesis of amides from nitroarenes and carboxylic acids via CO-mediated reduction

• Direct carbon monoxide mediated method for synthesis of amides from nitroarenes was developed. • No solid waste is generated during the reaction. • Simple Ru 3 (CO) 12 is the most efficient catalyst for this transformation working at PPM-level. • Kinetic study revealed a mixed order behavior of the developed process. A highly efficient direct carbon monoxide-mediated protocol for converting nitroarenes and carboxylic acids to amides was developed. Investigation of the reaction kinetics and a Hammett study allowed us to reveal the reaction mechanism and the best reaction conditions. An observed apparent partial reaction order by nitroarene in this reaction is 0.5 indicating the switch of the rate-determining step during the course of the reaction. A highly valuable Vorinostat precursor with 99% purity was synthesized in a quantitative yield without any purification; the E-factor of the process was 0.35, which fits to the multiton chemistry reactions. All substrate scope was prepared using the simple Ru 3 (CO) 12 as a catalyst, and TON up to 44,400 was achieved.

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Publication Details

Journal
Journal of Catalysis
Published
2025-02-22
DOI
https://doi.org/10.1016/j.jcat.2025.116042
Citations
5
Primary Topic
Asymmetric Hydrogenation and Catalysis
Type
article
Field-Weighted Citation Impact
2.69

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article

Direct synthesis of amides from nitroarenes and carboxylic acids via CO-mediated reduction

Mikhail A. Losev, Oleg I. Afanasyev, Denis Chusov
5 citations
Journal of Catalysis
Asymmetric Hydrogenation and Catalysis
2.69
article

Direct synthesis of amides from nitroarenes and carboxylic acids via CO-mediated reduction

Mikhail A. Losev, Oleg I. Afanasyev, Denis Chusov
article en
5 citations

Abstract

• Direct carbon monoxide mediated method for synthesis of amides from nitroarenes was developed. • No solid waste is generated during the reaction. • Simple Ru 3 (CO) 12 is the most efficient catalyst for this transformation working at PPM-level. • Kinetic study revealed a mixed order behavior of the developed process. A highly efficient direct carbon monoxide-mediated protocol for converting nitroarenes and carboxylic acids to amides was developed. Investigation of the reaction kinetics and a Hammett study allowed us to reveal the reaction mechanism and the best reaction conditions. An observed apparent partial reaction order by nitroarene in this reaction is 0.5 indicating the switch of the rate-determining step during the course of the reaction. A highly valuable Vorinostat precursor with 99% purity was synthesized in a quantitative yield without any purification; the E-factor of the process was 0.35, which fits to the multiton chemistry reactions. All substrate scope was prepared using the simple Ru 3 (CO) 12 as a catalyst, and TON up to 44,400 was achieved.

Journal of CatalysisVol. 445
National Research University Higher School of Economics (RU), A. N. Nesmeyanov Institute of Organoelement Compounds (RU)
Ministry of Education and Science of the Russian Federation, Russian Science Foundation
Openalex Percentile: Top 11%
Asymmetric Hydrogenation and Catalysis
2.69
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