Sperandio Céline, Rodriguez Jean, Quintard Adrien
Aix Marseille Univ , CNRS , Centrale Marseille , iSm2 , Marseille , France . Email:
Chem Sci. 2019 Dec 27;11(6):1629-1635. doi: 10.1039/c9sc05196a. eCollection 2020 Feb 14.
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.
氟能够赋予有机分子独特的性质，但天然有机氟源的稀缺使得开发新的合成方法变得非常必要。使用手性BOX/铜组合，已开发出全氟醛的对映选择性脱羧羟醛缩合反应。最值得注意的是，该反应在温和条件下进行且对映选择性高，能够在单一合成操作中生成酮二醇，而酮二醇是关键的全氟1,3,5 -三醇的前体。此外，与氯醛进行的反应验证了基于空间相互作用提出的过渡态模型，并首次实现了具有重要合成用途的六氯代酮二醇的对映选择性合成。全氟1,3,5 -三醇形成中心氢键框架的能力使得其能够与阴离子强烈配位，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。
