Titanocene(III)-Catalyzed Three-Component Reaction of Secondary Amides, Aldehydes, and Electrophilic Alkenes.
Titanocene(III)-Catalyzed Three-Component Reaction of Secondary Amides, Aldehydes, and Electrophilic Alkenes.
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二茂钛 (III) 催化仲酰胺、醛和亲电烯烃的三组分反应。
DOI：
10.1002/anie.201506907
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Huang Pei-Qiang
中科院分区：
文献类型：
--
作者：
Zheng Xiao;He Jiang;Li Heng-Hui;Wang Ao;Dai Xi-Jie;Wang Ai-E;Huang Pei-Qiang
公开了仲酰胺、脂族醛和亲电子烯烃的非极性曼尼希型反应。该反应的特点是通过茂钛催化的仲酰胺和醛的缩合产物与亲电烯烃的自由基偶联一锅形成C-N和C-C键。N-取代的γ-酰胺基酸衍生物和γ-酰胺基酮可以通过本方法有效地制备。酮酰胺和亲电子烯烃之间的反应的扩展允许哌啶骨架与α-氨基季碳中心的快速组装。它的合成效用已被证明是由一个简单的建设三环核心的海洋生物碱，如柱孢菌素C和polycitorol A。
An umpolung Mannich-type reaction of secondary amides, aliphatic aldehydes, and electrophilic alkenes has been disclosed. This reaction features the one-pot formation of C-N and C-C bonds by a titanocene-catalyzed radical coupling of the condensation products, from secondary amides and aldehydes, with electrophilic alkenes. N-substituted γ-amido-acid derivatives and γ-amido ketones can be efficiently prepared by the current method. Extension to the reaction between ketoamides and electrophilic alkenes allows rapid assembly of piperidine skeletons with α-amino quaternary carbon centers. Its synthetic utility has been demonstrated by a facile construction of the tricyclic core of marine alkaloids such as cylindricine C and polycitorol A.