Thiourea Catalyzed Enantioselective Fluorination

描述(由申请人提供)：拟议的项目将使一系列有机底物类别的催化、对映选择性氟化成为可能，包括合成具有挑战性的、完全取代的氟化碳立体中心。使用多功能的、双功能的 硫脲催化剂应允许多种底物结合模式，从而能够使用广泛的底物和氟化试剂。硫脲催化剂与氟化剂结合的倾向将通过光谱方法进行评估，从而深入了解试剂活化的强度和方式。将催化剂/试剂组合应用于底物类别，如醛和酮酯，将允许对映体选择性地合成多种含氟化合物。酮酯氟化与亚胺催化的结合将使快速组装分子复杂性的强大多米诺骨牌转化成为可能。建议的催化剂和氟化试剂的变化将允许硅酮缩醛的对映选择性氟化，得到氟化酯。

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.