Organocatalytic Chemo- and Regioselective Oxyarylation of Styrenes via a Cascade Reaction: Remote Activation of Hydroxyl Groups

• Published in: Journal of organic chemistry 2014-07, Vol.79 (13), p.6143-6152
• Main Authors: Zhang, Yu-Chen, Jiang, Fei, Wang, Shu-Liang, Shi, Feng, Tu, Shu-Jiang
• Format: Article
• Language: English
• Subjects: Catalysis; Hydrogen Bonding; Hydroxyl Radical - chemistry; Molecular Structure; Naphthalenes - chemistry; Phosphoric Acids - chemistry; Stereoisomerism; Styrenes - chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo500859b

The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.