Control of Activation Mode To Achieve Diastereodivergence in Asymmetric Syntheses of Chiral Spiropiperidinone Derivatives

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• 作者：Xiang Li ; Wei Huang ; Yan-Qing Liu ; Jing-Wen Kang ; Dan Xia ; Gu He ; Cheng Peng ; Bo Han
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：January 6, 2017
• 年：2017
• 卷：82
• 期：1
• 页码：397-406
• 全文大小：575K
• ISSN：1520-6904

文摘

An efficient organocatalytic cascade reaction has been developed involving a Michael–hemiaminalization relay for the asymmetric synthesis of spiropiperidinone derivatives bearing adjacent quaternary and tertiary chiral centers via LUMO or HOMO activation. Importantly, this methodology demonstrates that applying distinct activation modes to different substrates in the same reaction can diverge diastereoselectivity. To our knowledge, this is also one of the few published cases of primary amine catalytic [3 + 3] cycloaddition reactions involving α-branched β-ketoamides.