Asymmetric synthesis of 1,2-dioxolane-3-acetic acids: Synthesis and configurational assignment of plakinic acid A
Asymmetric synthesis of 1,2-dioxolane-3-acetic acids: Synthesis and configurational assignment of plakinic acid A
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DOI：
10.1021/jo0522254
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发表时间：
2006-03-17
影响因子：
3.6
通讯作者：
Dussault, PH
中科院分区：
文献类型：
--
作者：
Dai, P;Trullinger, TK;Dussault, PH
[图片]首次报道了1,2-二恶氧烷-3-乙酸的不对称合成。主要特征包括过氧化氢对映体富集的氧烷的立体选择性开孔，生成的4-羟基-2-烷醇转化为3-烷氧基-1,2-二恶氧烷，以及刘易斯酸介导的后者与硫酯硅基烯酮缩醛的同源化。该方法以3,5-二甲基-5-十六烷基-1,2-二恶烷-3-乙酸（1a）为模型，这是一种未命名的天然产物，并将优化策略应用于合成铂酸A(2)的四个立体异构体，允许这种不完全表征的天然产物的构型分配。
[GRAPHICS]The first asymmetric synthesis of 1,2-dioxolane-3-acetic acids is reported. Key features include the stereoselective opening of enantiomerically enriched oxetanes by hydrogen peroxide, conversion of the resulting 4-hydroperoxy-2-alkanols to 3-alkoxy-1,2-dioxolanes, and Lewis acid mediated homologation of the latter with a thioester silyl ketene acetal. The approach is modeled on 3,5-dimethyl-5-hexadecyl-1,2-dioxolane-3-acetic acid (1a), an unnamed natural product, and an optimized strategy is applied to the synthesis of four stereoisomers of plakinic acid A (2), allowing a configurational assignment of this incompletely characterized natural product.