Ishida Yasuhiro, Nakamura Itaru, Terada Masahiro
Department of Chemistry, Graduate School of Science , Tohoku University , Sendai 980-8578 , Japan.
Research and Analytical Center for Giant Molecules, Graduate School of Science , Tohoku University , Sendai 980-8578 , Japan.
J Am Chem Soc. 2018 Jul 18;140(28):8629-8633. doi: 10.1021/jacs.8b03669. Epub 2018 Jun 25.
Multisubstituted ortho-anisidines were efficiently synthesized via cationic N-heterocyclic carbene-Cu-catalyzed domino rearrangement of N-methoxyanilines that possess an electron-donating functional group, such as an alkyl or an aryl group, at the ortho position. The reaction proceeded first through a [1,3]-rearrangement of the methoxy group to the ortho position bound to the electron-donating substituent, followed by a semipinacol type [1,2]-rearrangement of the electron-donating group from the ortho to the meta position. Mechanistic studies suggest that both rearrangement reactions are promoted by a cationic Cu catalyst.
通过阳离子型N-杂环卡宾-铜催化的N-甲氧基苯胺的多米诺重排反应，高效合成了多取代邻甲氧基苯胺。该反应中，N-甲氧基苯胺在邻位带有供电子官能团，如烷基或芳基。反应首先通过甲氧基的[1,3]重排至与供电子取代基相连的邻位，随后供电子基团从邻位到间位发生半频哪醇型[1,2]重排。机理研究表明，两种重排反应均由阳离子铜催化剂促进。
