Concise Synthesis of (+)-[13 C4 ]-Anatoxin-a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion.
Concise Synthesis of (+)-[13 C4 ]-Anatoxin-a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion.
复制标题
通过环亚胺离子的动态动力学拆分简明合成 ( )-[13 C4 ]-Anatoxin-a。
DOI：
10.1002/anie.202004464
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Zakarian,Armen
中科院分区：
文献类型：
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作者：
Lacharity,JacobJ;Mailyan,ArturK;Chen,KarenY;Zakarian,Armen
以市售的[13 C4]-乙酰乙酸乙酯（[13 C4]-15）为原料，开发了[13 C4]-类毒素-a（[13 C4]-1）的不对称全合成方法。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，提供了0.110 g这种内标物，用于检测和精确定量淡水中的类毒素a。 该合成的一个亮点是利用环状亚胺离子外消旋在对映选择性Morita-Baylis-Hillman（MBH）环化中实现动态动力学拆分的方法。
An asymmetric total synthesis of [13C4]‐anatoxin‐a ([13C4]‐1) has been developed from commercially available ethyl [13C4]‐acetoacetate ([13C4]‐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.