Asymmetric Organocatalytic Intramolecular Aza-Michael Addition of Enone Carbamates: Catalytic Enantioselective Access to Functionalized 2-Substituted Piperidines
Asymmetric Organocatalytic Intramolecular Aza-Michael Addition of Enone Carbamates: Catalytic Enantioselective Access to Functionalized 2-Substituted Piperidines
复制标题
烯酮氨基甲酸酯的不对称有机催化分子内 Aza-Michael 加成：催化对映选择性获得功能化 2-取代哌啶
DOI：
10.1002/adsc.201100282
复制
发表时间：
2011-10-01
影响因子：
5.4
通讯作者：
Fan, Chun-An
中科院分区：
文献类型：
--
作者：
Liu, Jian-Dong;Chen, Ying-Chun;Fan, Chun-An
通过烯酮氨基甲酸酯的有机催化对映选择性分子内氮杂迈克尔加成，策略性地获得了具有合成用途的官能化2-取代哌啶，其中含有侧酮基团，其中在不对称双功能有机催化中揭示了烯酮部分作为迈克尔受体和氨基甲酸酯部分作为迈克尔供体的新型内部底物组合。这种杂原子共轭加成是通过使用催化手性金鸡纳基伯叔二胺和非手性布朗斯台德酸实现的，大部分以高收率和良好到优异的立体控制（高达 99% ee）进行。该反应提供了另一种催化不对称方法，用于在功能化的 2-取代哌啶中安装立体含氮碳中心，从而开发出一些天然存在的生物活性 2-取代哌啶生物碱的直接且快速的合成方法。
The synthetically useful functionalized 2-substituted piperidines containing a lateral ketone group have been strategically accessed via an organocatalytic enantioselective intramolecular aza-Michael addition of enone carbamates, in which a novel internal substrate combination of the enone moiety as Michael acceptor and the carbamate moiety as Michael donor was revealed in asymmetric bifunctional organocatalysis. This heteroatom conjugate addition, which was realized by using a catalytic chiral Cinchona-based primary-tertiary diamine and an achiral Bronsted acid, mostly proceeded in high yield and good to excellent stereocontrol (up to 99% ee). This reaction provides an alternative catalytic asymmetric method for installing the stereogenic nitrogen-containing carbon center in functionalized 2-substituted piperidines, leading to the development of a straightforward and expeditious synthesis of some naturally occurring bioactive 2-substituted piperidine alkaloids.