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Updated: Sep 14, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Au-Catalyzed Aerobic Dehydrogenative Aromatization to m-Phenylenediamine Derivatives via Product Selectivity Control
Heizo Kimura1, Takafumi Yatabe1,2, Kazuya Yamaguchi1
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
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.
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