通过环状亚铵离子的动态动力学拆分简洁合成 (+)-[C]-anatoxin-a。
Concise Synthesis of (+)-[ C ]-Anatoxin-a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion.
机构信息
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA, 93106-9510, USA.
出版信息
Angew Chem Int Ed Engl. 2020 Jul 6;59(28):11364-11368. doi: 10.1002/anie.202004464. Epub 2020 May 11.
Abstract
An asymmetric total synthesis of [ C ]-anatoxin-a ([ C ]-1) has been developed from commercially available ethyl [ C ]-acetoacetate ([ C ]-15). The unique requirements associated with isotope incorporation inspired a new, robust, and highly scalable route, providing access to 0.110 g of this internal standard for use in the detection and precise quantification of anatoxin-a in freshwater. A highlight of the synthesis is a method that leverages a cyclic iminium ion racemization to achieve dynamic kinetic resolution in an enantioselective Morita-Baylis-Hillman (MBH) cyclization.
摘要
已开发出一种从商业可得的乙基[C]-乙酰乙酸酯([C]-15)不对称全合成[C]-anatoxin-a([C]-1)的方法。与同位素掺入相关的独特要求激发了一种新的、稳健的、高度可扩展的路线，该路线提供了 0.110g 的这种内标，用于检测和精确量化淡水中的anatoxin-a。该合成的一个亮点是利用环状亚氨基离子外消旋化来实现对映选择性 Morita-Baylis-Hillman (MBH) 环化反应的动态动力学拆分的方法。
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