Synthesis of meta-Substituted Anilines via Copper-Catalyzed [1,3]-Methoxy Rearrangement
Synthesis of meta-Substituted Anilines via Copper-Catalyzed [1,3]-Methoxy Rearrangement
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DOI：
10.1021/acs.orglett.0c01009
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发表时间：
2020-05-15
期刊：
影响因子：
5.2
通讯作者：
Terada, Masahiro
中科院分区：
文献类型：
--
作者：
Nakamura, Itaru;Tashiro, Hiroki;Terada, Masahiro
通过铜催化的N-甲氧基苯胺的[1，3]-甲氧基重排反应和亲核试剂与原位生成的邻苯二酚亚胺的Michael加成反应，有效地合成了间位取代苯胺。本反应对对位取代基如乙烯基、甲硫基、酯基和溴基以及碳亲核试剂如1，3，5-三甲氧基苯、N-甲基吲哚和丙二酸二甲酯表现出优异的适用性。因此，本发明的重排可以解决源于氧化反应的问题，例如使用化学计量量的氧化剂和吸电子基团的低相容性。
meta-Substituted anilines were efficiently synthesized via copper-catalyzed [1,3]-methoxy rearrangement of N-methoxyanilines followed by Michael addition of nucleophiles to the in situ generated ortho-quinol imine. The present reaction exhibits excellent applicability of para-substituents, such as vinyl, methylthio, ester, and bromo, and carbon nucleophiles, such as 1,3,5-trimethoxybenzene, N-methylindole, and dimethyl malonate. Thus, the present rearrangement can resolve problems stemming from oxidation reactions, such as the use of stoichiometric amounts of oxidants and low compatibility of electron-withdrawing groups.