Friedel鈥揅rafts Coupling of Electron-Deficient Benzoylacetones Tuned by Remote Electronic Effects

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• 作者：Hongmei Luo ; Ling Pan ; Xianxiu Xu ; Qun Liu
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：August 21, 2015
• 年：2015
• 卷：80
• 期：16
• 页码：8282-8289
• 全文大小：519K
• ISSN：1520-6904

文摘

Acid-catalyzed electrophilic aromatic substitution for C鈥揅 bond formation, commonly referred to as the Friedel鈥揅rafts reaction in recognition of its discoverers, has been one of the most useful reactions in organic chemistry for over a century. However, the Friedel鈥揅rafts reaction cannot occur on a benzene ring having a strongly electron withdrawing group, such as an acyl group, which deactivates the aromatic ring toward electrophilic substitutions and remains a major challenge. Herein, the synthesis of naphthoquinones and 1,3-indandiones, bearing two acyl groups at positions ortho to each other on a benzene ring, are demonstrated by means of copper-catalyzed intramolecular aerobic oxidative acylation of benzoylacetone derivative precursors. This unusual Friedel鈥揅rafts reaction reveals a new activation mode for the in situ polarity reverse of an electron-deficient aromatic ring to a reactive, electron-rich ring tuned by remote electronic effects.