Bicyclic- and tricyclic-β-lactones via organonucleophile-promoted bis-cyclizations of keto acids:: Enantioselective synthesis of (+)-dihydroplakevulin
Bicyclic- and tricyclic-β-lactones via organonucleophile-promoted bis-cyclizations of keto acids:: Enantioselective synthesis of (+)-dihydroplakevulin
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DOI：
10.1021/ol061816t
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发表时间：
2006-09-14
期刊：
影响因子：
5.2
通讯作者：
Romo, Daniel
中科院分区：
文献类型：
--
作者：
Henry-Riyad, Huda;Lee, Changsuk;Romo, Daniel
描述了一种高度非对映选择性，亲核促进的双环化过程，采用易于获得和处理的酮酸底物。这种方法提供了简明的途径来获得含有叔甲醇中心和季碳的双环和三环- β -内酯，大大扩展了以前从醛酸底物中获得双环- β -内酯的途径。该方法的实用性被应用于(+)-二氢plakevulin a的对映选择性合成。这一过程和相关过程可能揭示了[2+2]环加成和亲核催化的醛醇内酯化（NCAL）反应流形之间的微妙相互作用。
A highly diastereoselective, nucleophile-promoted bis-cyclization process, employing readily available and tractable keto acid substrates, is described. This methodology provides concise access to bicyclic- and tricyclic-beta-lactones bearing tertiary carbinol centers and quaternary carbons, greatly extending the scope of previous routes to bicyclic-beta-lactones from aldehyde acid substrates. The utility of the method was demonstrated by application to an enantioselective synthesis of (+)-dihydroplakevulin A. This and related processes may be revealing a subtle interplay between [2+2] cycloaddition and nucleophile-catalyzed aldol lactonization (NCAL) reaction manifolds.