Development of copper-catalyzed enantioselective decarboxylative aldolization for the preparation of perfluorinated 1,3,5-triols featuring supramolecular recognition properties.,Chemical Science

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Development of copper-catalyzed enantioselective decarboxylative aldolization for the preparation of perfluorinated 1,3,5-triols featuring supramolecular recognition properties.
Chemical Science ( IF 7.6 ) Pub Date : 2019-12-27 , DOI: 10.1039/c9sc05196a
Céline Sperandio ₁ , Jean Rodriguez ₁ , Adrien Quintard ₁

Affiliation

Fluorine is able to confer unique properties to organic molecules but the scarcity of natural organofluorine sources renders the development of new synthetic methods highly desirable. Using a chiral BOX/Cu combination, enantioselective decarboxylative aldolization of perfluorinated aldehydes has been developed. Most notably, the reaction occurring under mild conditions and with high enantiocontrol can create ketodiols in one single synthetic operation, which are precursors of crucial perfluorinated 1,3,5-triols. In addition, the reaction performed with chloral, validates the proposed transition state model based on steric interactions and provides the first enantioselective synthesis of hexachlorinated ketodiol of great synthetic utility. The ability of perfluorinated 1,3,5-triols to form a central hydrogen-bonding framework allows strong coordination of anions and the chirality obtained through the catalyst-controlled synthetic sequence demonstrates the selective chiral anion recognition ability of polyols.

中文翻译：

开发铜催化对映选择性脱羧醛醇缩合反应制备具有超分子识别特性的全氟 1,3,5-三醇。

氟能够赋予有机分子独特的性质，但天然有机氟来源的稀缺使得开发新的合成方法非常迫切。使用手性 BOX/Cu 组合，开发了全氟醛的对映选择性脱羧醛醇缩反应。最值得注意的是，在温和条件下发生的反应具有高对映体控制，可以在一次合成操作中产生酮二醇，这是关键的全氟化 1,3,5-三醇的前体。此外，与三氯乙醛进行的反应验证了所提出的基于空间相互作用的过渡态模型，并提供了具有巨大合成实用性的六氯化酮二醇的第一个对映选择性合成。全氟化1,3,5-三醇形成中心氢键框架的能力允许阴离子的强配位，并且通过催化剂控制的合成序列获得的手性证明了多元醇的选择性手性阴离子识别能力。

更新日期：2020-02-13

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