手性控制在亚胺和氰基丁二酸酐不对称 γ-内酰胺合成中的应用。
Stereocontrol in asymmetric γ-lactam syntheses from imines and cyanosuccinic anhydrides.
机构信息
Department of Chemistry, University of California, Davis , One Shields Avenue, Davis, California 95616, United States, and Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.
出版信息
Org Lett. 2013 Oct 4;15(19):5130-3. doi: 10.1021/ol402561q. Epub 2013 Sep 26.
Abstract
Computations (SCS-MP2//B3LYP) reveal that the asymmetric synthesis of highly substituted γ-lactams with three stereogenic centers, including one quaternary center, proceeds through a Mannich reaction between the enol form of the anhydride and the E-imine, followed by a transannular acylation. This new mechanistic picture accounts for both the observed reactivity and stereoselectivity. CH-O and hydrogen bonding interactions in the Mannich step and torsional steering effects in the acylation step are responsible for stereocontrol. It is demonstrated that this new mechanistic picture applies to the related reactions of homophthalic anhydrides with imines and presents new vistas for the design of a new reaction to access complex molecular architectures.
摘要
计算（SCS-MP2//B3LYP）表明，具有三个立体中心的高度取代的γ-内酰胺的不对称合成，包括一个季碳原子，通过酐的烯醇形式和 E-亚胺之间的Mannich 反应进行，然后进行环间酰化。这个新的机理图解释了观察到的反应性和立体选择性。Mannich 步骤中的 CH-O 和氢键相互作用以及酰化步骤中的扭转导向效应负责立体控制。证明这种新的机理图适用于与亚胺的同邻苯二甲酸酐的相关反应，并为设计新反应以获得复杂分子结构提供了新的视角。
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