Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, China.
Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University, Xiamen, Fujian, 361005, China.
Nat Commun. 2018 Jan 29;9(1):410. doi: 10.1038/s41467-017-02698-4.
Enantiopure vicinal amino alcohols and derivatives are essential structural motifs in natural products and pharmaceutically active molecules, and serve as main chiral sources in asymmetric synthesis. Currently known asymmetric catalytic protocols for this class of compounds are still rare and often suffer from limited scope of substrates, relatively low regio- or stereoselectivities, thus prompting the development of more effective methodologies. Herein we report a dual catalytic strategy for the convergent enantioselective synthesis of vicinal amino alcohols. The method features a radical-type Zimmerman-Traxler transition state formed from a rare earth metal with a nitrone and an aromatic ketyl radical in the presence of chiral N,N'-dioxide ligands. In addition to high level of enantio- and diastereoselectivities, our synthetic protocol affords advantages of simple operation, mild conditions, high-yielding, and a broad scope of substrates. Furthermore, this protocol has been successfully applied to the concise synthesis of pharmaceutically valuable compounds (e.g., ephedrine and selegiline).
对映纯偕氨基醇及其衍生物是天然产物和药物活性分子中的重要结构基序,也是不对称合成中的主要手性源。目前已知的此类化合物的不对称催化方法仍然很少,并且通常受到底物范围有限、区域或立体选择性相对较低的限制,因此需要开发更有效的方法。在此,我们报告了一种用于偕氨基醇的对映选择性汇聚合成的双催化策略。该方法的特点是在手性 N,N'-二氧杂环戊烷配体的存在下,由稀土金属与硝酮和芳基酮基自由基形成自由基型 Zimmerman-Traxler 过渡态。除了具有高对映选择性和非对映选择性外,我们的合成方案还具有操作简单、条件温和、产率高和底物范围广泛的优点。此外,该方案已成功应用于具有药用价值的化合物(如麻黄碱和司来吉兰)的简洁合成。