Fluorous Phase-Based Fluorescent Chiral Discrimination

基于氟相的荧光手性辨别

• 批准号: 1565627
• 负责人: Lin Pu
• 金额: $ 40.5万
• 依托单位: University of Virginia Main Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-04-01 至 2020-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565627&HistoricalAwards=false
• 关键词: Fluorous; Phase; Based; Fluorescent; Chiral

In this project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professor Lin Pu of the Department of Chemistry at University of Virginia is developing new enantioselective fluorescent sensors for the recognition of chiral amines in perfluorocarbon solvents (fluorous phase). These sensors are used to facilitate the high throughput screening of chiral catalysts for the asymmetric synthesis of chiral amines that are useful in the synthesis of organic compounds of pharmaceutical and biological importance. This project provides extensive education and training for graduate and undergraduate students in areas such as organic synthesis, spectroscopic study, and catalyst development. This group also participates in an outreach program to carry out chemistry-based demonstrations for elementary school students and teachers. This outreach program is dedicated to providing inquiry-based chemistry instruction at the elementary school level.Enantioselective fluorescent sensors containing perfluoroalkyl chains are expected to be more soluble in fluorous solvents than in common organic solvents. They are used to conduct the enantioselective fluorescent recognition of functional chiral amines such as diamines, amino alcohols and amino acids in fluorous solvents. Pseudoenantiomeric pairs of such sensors are prepared. In each pair there are two sensors having the opposite enantioselective fluorescent response with two distinctively different emission wavelengths upon interaction with the two enantiomers of a chiral amine substrate. These sensors are applied to chiral catalyst screening. A fluorous solution of a pseudoenantiomeric sensor pair are used to extract the products, generated from the chiral catalyst screening experiments conducted in common organic solvents or aqueous solution, into the fluorous phase. Because only the sensors and their adducts with the chiral products could be dissolved in the fluorous phase, the interference of other species such as reagents, catalysts and starting materials is minimized. Through fluorescent measurement, both the yield and enantiomeric composition of the chiral products is simultaneously determined. The structure of the sensors is modified in order to conduct the enantioselective fluorescent recognition of un-functionalized amines. The fluorous phase-based fluorescent detection of this project has potential to be automated to conduct high throughput catalyst screening. Under the direction of PI, graduate students and undergraduate students of diverse backgrounds are recruited to conduct research in organic synthesis, spectroscopic studies, and catalyst development. Students will learn many laboratory skills that are useful for their future employment and allow them to make contributions to the society.

在化学系化学结构、动力学机理B项目资助下，美国弗吉尼亚大学化学系林璞教授正在开发一种新型的对映选择性荧光传感器，用于全氟化碳溶剂（氟相）中手性胺的识别。 这些传感器用于促进用于手性胺的不对称合成的手性催化剂的高通量筛选，所述手性胺可用于合成具有药物和生物学重要性的有机化合物。 该项目为研究生和本科生提供广泛的教育和培训，如有机合成，光谱研究和催化剂开发。 该小组还参加了一个外展计划，为小学学生和教师进行基于化学的演示。 该推广计划致力于在小学阶段提供基于探究的化学教学。含有全氟烷基链的对映选择性荧光传感器预计在氟溶剂中比在普通有机溶剂中更易溶解。 它们在氟溶剂中对二胺、氨基醇、氨基酸等功能性手性胺进行对映选择性荧光识别。 制备此类传感器的假对映体对。 在每对中，存在两个传感器，其在与手性胺底物的两种对映体相互作用时具有相反的对映选择性荧光响应，具有两个明显不同的发射波长。 这些传感器可用于手性催化剂的筛选。 使用假对映体传感器对的氟溶液将在常见有机溶剂或水溶液中进行的手性催化剂筛选实验产生的产物萃取到氟相中。 由于只有传感器及其与手性产物的加合物可以溶解在氟相中，因此其他物质如试剂、催化剂和起始材料的干扰最小化。 通过荧光测量，同时测定了手性产物的产率和对映体组成。 对传感器的结构进行了修饰，以进行非官能化胺的对映选择性荧光识别。 本计画的荧光相位检测法具有自动化进行高通量催化剂筛选的潜力。 在PI的指导下，招募不同背景的研究生和本科生进行有机合成，光谱研究和催化剂开发的研究。学生将学习许多实验室技能，这些技能对他们未来的就业非常有用，并使他们能够为社会做出贡献。