2025-07-25 東京大学
酸化セリウム担持金ナノ粒子触媒による脱水素芳香環形成を経るメタフェニレンジアミン類の選択合成
＜関連情報＞
- https://www.t.u-tokyo.ac.jp/press/pr2025-07-25-001
- https://www.t.u-tokyo.ac.jp/hubfs/press-release/2025/0725/001/text.pdf
- https://pubs.acs.org/doi/10.1021/jacs.4c12043
Au触媒を用いた好気性脱水素化芳香化反応によるm-フェニレンジアミン誘導体の合成：製品選択性の制御を通じて Au-Catalyzed Aerobic Dehydrogenative Aromatization to m-Phenylenediamine Derivatives via Product Selectivity Control
Heizo Kimura,Takafumi Yatabe,and Kazuya Yamaguchi
Journal of the American Chemical Society Published: July 24, 2025
DOI:https://doi.org/10.1021/jacs.4c12043
Abstract
m-Disubstituted arenes are important in various fields but difficult to be directly synthesized by classical methods in the case of two electron-donating substituents due to the o,p-orientation. Dehydrogenative aromatization from nonaromatic cyclohexenone motifs and nucleophiles via 1,2- and 1,4-addition to produce m-disubstituted arenes is promising as the novel process overcoming the intrinsic problems derived from using aromatic compounds as the substrates; however, there are no reports on tandem oxidation involving dehydrogenative aromatization for one-step synthesis via simultaneous 1,2- and 1,4-addition or m-phenylenediamine derivative synthesis because of the quite difficult product selectivity control. Here, by utilizing the unique dehydrogenation catalysis of CeO2-supported Au nanoparticles, we have developed one-step synthesis of various m-phenylenediamine derivatives via selective aerobic dehydrogenative aromatization from cyclohexenone motifs and secondary amines. In addition, the product selectivity switch to enaminones or N,N-disubstituted anilines was also achieved by tuning the reaction conditions.
