Asymmetric Formal Aza-Diels–Alder Reaction of Trifluoromethyl Hemiaminals with Enones Catalyzed by Primary Amines

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• 作者：Sheng Zhang ; Lide Cha ; Lijun Li ; Yanbin Hu ; Yanan Li ; Zhenggen Zha ; Zhiyong Wang
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：April 15, 2016
• 年：2016
• 卷：81
• 期：8
• 页码：3177-3187
• 全文大小：556K
• 年卷期：0
• ISSN：1520-6904

文摘

A primary amine-catalyzed asymmetric formal aza-Diels–Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels–Alder product.