Thiourea Catalyzed Enantioselective Fluorination

描述（由申请人提供）：拟议的项目将使催化，对映选择性的一系列有机底物类，包括具有挑战性的，完全取代的氟化碳立体中心的合成。使用多功能、双功能 硫脲催化剂应允许多种底物结合模式，使得能够使用宽范围的底物和氟化试剂。硫脲催化剂结合氟化剂的倾向将通过光谱方法进行评估，提供深入了解试剂活化的强度和模式。将催化剂/试剂组合应用于底物类别如醛和戊-酮酯将允许对映选择性合成通用氟化化合物。组合用亚胺催化的β-酮酯的合成将使分子复杂性的快速组装成为可能。所提出的催化剂和氟化试剂的变化将允许甲硅烷基烯酮缩醛的对映选择性加成，从而提供氟化酯。

DESCRIPTION (provided by applicant): The proposed project will enable the catalytic, enantioselective fluorination of a range of organic substrate classes, including the synthesis of challenging, fully substituted fluorinated carbon stereocenters. The use of versatile, bifunctional thiourea catalysts should allow for a variety of substrate binding modes, enabling the use of a wide range of substrates and fluorinating reagents. The propensity of thiourea catalysts to bind to fluorinating agents will be evaluated via spectroscopic methods, providing insight into the strength and mode of reagent activation. Application of the catalyst/reagent combination to substrate classes such as aldehydes and ¿-ketoesters will allow for the enantioselective synthesis of versatile fluorinated compounds. Combination of ¿-ketoester fluorination with iminium catalysis will enable powerful domino transformations for the rapid assembly of molecular complexity. Proposed variation of the catalyst and fluorinating reagent will allow for the enantioselective fluorination of silyl ketene acetals, affording ¿-fluorinated esters.