Bioinspired Electrolysis for Green Molecular Transformations of Organic Halides Catalyzed by B12 Complex

Hisashi Shimakoshi, Yoshio Hisaeda

研究成果: Contribution to journalReview article査読

抄録

Naturally-occurring B12-dependent enzymes catalyze various molecular transformations that are of particular interest from the viewpoint of biological chemistry as well as synthetic organic chemistry. Inspired by the unique property of the B12-dependent enzymes, various catalytic reactions have been developed using its model complex. Among the B12 model complexes, heptamethyl cobyrinate, synthesized from natural vitamin B12, is highly soluble in various organic solvents and a redox active cobalt complex with an excellent catalysis in electroorganic synthesis. The electrochemical dechlorination of pollutant organic chlorides, such as DDT, was effectively catalyzed by the B12 complex. Modification of the electrode surface by the sol-gel method to immobilize the B12 complex was also developed. The B12 modified electrodes were effective for the dehalogenation of organic halides with high turnover numbers based on the immobilized B12 complex. Electrolysis of an organic halide catalyzed by the B12 complex provided dechlorinated products under anaerobic conditions, while the electrolysis under aerobic conditions afforded oxygen incorporated products, such as an ester and amide along with dechlorination. Benzotrichloride was transformed into ethylbenzoate or N,N-diethylbenzamide in the presence of ethanol or diethylamine, respectively. This amide formation was further expanded to a unique paired electrolysis. Electrochemical reductions of an alkene and alkyne were also catalyzed by the B12 complex. A cobalt-hydrogen complex should be formed as a bioinspired intermediate. Using the B12 complex, light-assisted electrosynthesis was also developed to save the applied energy.

本文言語英語
ジャーナルChemical Record
DOI
出版ステータス受理済み/印刷中 - 2021

All Science Journal Classification (ASJC) codes

  • 化学 (全般)
  • 生化学
  • 化学工学(全般)
  • 材料化学

フィンガープリント

「Bioinspired Electrolysis for Green Molecular Transformations of Organic Halides Catalyzed by B<sub>12</sub> Complex」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル