Electrocatalytic Hydrogenation of Pyridines and Other Nitrogen-Containing Aromatic Compounds.

Autor: Shida N; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.; Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.; PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan., Shimizu Y; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan., Yonezawa A; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan., Harada J; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan., Furutani Y; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan., Muto Y; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan., Kurihara R; Research Center for Solar Energy Chemistry, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan., Kondo JN; Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, Kanagawa 225-8503, Japan., Sato E; Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan., Mitsudo K; Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan., Suga S; Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan., Iguchi S; Graduate School of Engineering, Kyoto University, Kyoto daigaku-katsura, Nishikyo-ku, Kyoto 615-8530, Japan., Kamiya K; Research Center for Solar Energy Chemistry, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan.; Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan., Atobe M; Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.; Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Nov 06; Vol. 146 (44), pp. 30212-30221. Date of Electronic Publication: 2024 Oct 07.
DOI: 10.1021/jacs.4c09107
Abstrakt: The production of cyclic amines, which are vital to the pharmaceutical industry, relies on energy-intensive thermochemical hydrogenation. Herein, we demonstrate the electrocatalytic hydrogenation of nitrogen-containing aromatic compounds, specifically pyridine, at ambient temperature and pressure via a membrane electrode assembly with an anion-exchange membrane. We synthesized piperidine using a carbon-supported rhodium catalyst, achieving a current density of 25 mA cm -2 and a current efficiency of 99% under a circular flow until 5 F mol -1 . Quantitative conversion of pyridine into piperidine with 98% yield was observed after passing 9 F mol -1 , corresponding to 65% of current efficiency. The reduction of Rh oxides on the catalyst surface was crucial for catalysis. The Rh(0) surface interacts moderately with piperidine, decreasing the energy required for the rate-determining desorption step. The proposed process is applicable to other nitrogen-containing aromatic compounds and could be efficiently scaled up. This method presents clear advantages over traditional high-temperature and high-pressure thermochemical catalytic processes.
Databáze: MEDLINE
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