Solid-Phase Biomimetic Synthesis of Polyketide
Solid-Phase Biomimetic Synthesis of Polyketide
复制标题
聚酮化合物的固相仿生合成
DOI：
10.1021/acs.joc.1c02441
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Kudo Kazuaki
中科院分区：
文献类型：
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作者：
Takeuchi Yuta;Akagawa Kengo;Kudo Kazuaki
固相仿生合成聚酮已发展起来。该方法包括（i）通过与丙二酸半硫酯的脱羧克莱森缩合使树脂结合的羧酸的碳链延长，（ii）逐步转化所得的β-酮硫酯，以及（iii）水解硫酯以再生羧酸用于下一个迭代循环。比色试验可用于方便地监测固相反应;孔雀石绿色（碱性染料）和氯化铁（III）分别成功地检测到羧酸和β-酮硫酯。凝胶相~（13）C核磁共振谱也可用来证实底物的固定化过程。将建立的方法应用于天然产物木吡喃酮C和醉椒素的合成。该方法可进一步推广到以催化非对映选择性不对称转移氢化为关键步骤合成（R）-醉椒素。
Solid-phase biomimetic polyketide synthesis has been developed. This method is composed of (i) carbon chain elongation of resin-bound carboxylic acid via decarboxylative Claisen condensation with malonic acid half thioester, (ii) stepwise transformation of the resulting β-ketothioester, and (iii) hydrolysis of thioester to regenerate the carboxylic acid for the next iteration cycle. Colorimetric tests were available for convenient monitoring of the solid-phase reactions; malachite green (basic dye) and iron(III) chloride successfully detected the carboxylic acid and the β-ketothioester, respectively. In addition, gel-phase13C NMR could be utilized to confirm the progress of substrate immobilization. The established method was applied to the synthesis of the natural products, xylapyrone C and kavain. The present method could be further extended to the synthesis of (R)-kavain with catalytic diastereoselective asymmetric transfer hydrogenation as a key step.