Alkynylogation and transformative fluorination in synthesis

合成中的炔基化和转化氟化

• 批准号: 0809683
• 负责人: Gerald Hammond
• 金额: --
• 依托单位: University of Louisville Research Foundation Inc
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-08-01 至 2011-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0809683&HistoricalAwards=false
• 关键词: Alkynylogation; transformative; fluorination; synthesis

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Frederick Luzzio at the University of Louisville to investigate alkynylogation in order to promote the transmission of electronic effects between a nucleophilic or electrophilic center through the intermediacy of a triple bond, and the conversion of hydrofluorocarbons (HFCs) into functionalized fluorinated building blocks through C-F activation of some fluorines within the molecule. The alkynylogation effects will be studied using a triple bond extended aldol (alkynylogous aldol) reaction as a working model, utilizing modern synthetic tools capable of controlling the regio- and stereochemistry. Specifically, the effect of size and Lewis acidity of the cation counterion of a base on the gamma-directed alkynylogous aldol reaction will be investigated; the effects of Lewis acid on the regio- and stereoselectivity of Mukaiyama type alkynylogous aldol reaction, and the reaction of silylketene acetals with electrophiles. Transformative fluorination will be pursued through the functionalization of industrially available, ecologically benign, three- or four-carbon HFCs by selectively removing fluorine, utilizing C-F bond activation reactions. A second generation of difluoropropargyl synthons will also be developed utilizing environmentally friendly reagents and conditions, capable of engendering cyclic precursors fitted with synthetic handles that maximize structural diversity. This research aims for practical approaches, and environmentally friendly uses of materials and for organic synthesis. The project will train a younger generation of chemists in synthesis and organofluorine chemistry and advance the education of underrepresented minorities.

无机，生物无机和有机化学计划的这一奖项支持路易斯维尔大学的Frederick Luzzio教授研究炔基化，以促进亲核或亲电中心之间的电子效应通过三键的中介作用的传递，以及氢氟烃（HFC）通过C-分子内某些氟的活化。 炔基化效应将使用三键扩展的羟醛（炔基羟醛）反应作为工作模型进行研究，利用现代合成工具能够控制区域和立体化学。具体而言，将研究碱的阳离子抗衡离子的大小和刘易斯酸性对γ-定向炔基羟醛反应的影响;刘易斯酸对Mukaiyama型炔基羟醛反应的区域和立体选择性的影响，以及硅烷基烯酮缩醛与亲电试剂的反应。将通过利用C-F键活化反应，选择性地去除氟，使工业上可获得的、生态上无害的三碳或四碳氢氟碳化合物功能化，从而实现变革性的氢氟碳化合物。 还将利用环境友好的试剂和条件开发第二代二氟炔丙基二酮，能够产生配有最大化结构多样性的合成手柄的环状前体。这项研究的目的是实用的方法，和环境友好的使用材料和有机合成。 该项目将培训合成和有机氟化学方面的年轻一代化学家，并促进代表性不足的少数民族的教育。