alpha-Fluoro-gamma-Substituted Allylphosphonate: A Novel Vinyl Fluoride Precursor

α-氟-γ-取代的烯丙基膦酸酯：一种新型氟乙烯前体

• 批准号: 9122304
• 负责人: Gerald Hammond
• 金额: $ 11.94万
• 依托单位: University of Massachusetts, Dartmouth
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-01-01 至 1995-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9122304&HistoricalAwards=false
• 关键词: alpha; Fluoro; gamma; Substituted; Allylphosphonate

Incorporation of fluorine in organic molecules modifies their chemical and biological properties. Many of the available fluorinating agents are non-specific and/or too difficult to handle. One solution to this problem is the use of fluorine-containing smaller molecules that can act as building blocks in the synthesis of more complex organic molecules. Specifically new syntheses of vinyl fluorides from a common precursor, alpha-fluoro-gamma-substituted allylphosphonate, will be developed. This precursor will permit the introduction of fluorine on the olefinic carbon in alpha, beta-unsaturated carbonyl compounds, and in conjugated dienals. The initial introduction of fluorine on the allylphosphonate will be done using a well-known reagent, diethylaminosulfur trifluoride (DAST). The methodology employed will utilize an electrophilic phosphorus reagent as a way to incorporate the phosphonate moiety in the vinyl fluoride precursor. This will result in different substituents around the phosphorus, which in turn will make it possible to obtain greater stereochemical control on the fluoroolefin formed by the Horner-Wadsworth-Emmons (HWE) condensation. %%% With this award, the Organic Synthesis Program will support the research of Dr. Gerald B. Hammond at the University of Massachusetts, Dartmouth. The research will explore the development of new ways to introduce a fluorine into complex molecules under non-corrosive conditions. This should benefit research in biochemistry and medicine as well as in the chemical industry.

有机分子中掺入氟会改变其化学和生物特性。 许多可用的氟化剂是非特异性的和/或太难处理。 解决这个问题的一种方法是使用含氟较小的分子，这些分子可以作为合成更复杂有机分子的基础材料。 具体而言，将开发由共同前体α-氟-γ-取代的烯丙基膦酸酯合成氟乙烯的新方法。 该前体将允许在α、β-不饱和羰基化合物和共轭二醛中的烯属碳上引入氟。 最初在烯丙基膦酸酯上引入氟将使用众所周知的试剂三氟化二乙氨基硫（DAST）来完成。 所采用的方法将利用亲电磷试剂作为将膦酸酯部分掺入氟乙烯前体中的方式。 这将导致磷周围出现不同的取代基，从而可以对霍纳-沃兹沃斯-埃蒙斯（HWE）缩合形成的氟代烯烃获得更好的立体化学控制。 %%% 凭借这一奖项，有机合成计划将支持达特茅斯马萨诸塞大学 Gerald B. Hammond 博士的研究。 该研究将探索开发在非腐蚀条件下将氟引入复杂分子的新方法。 这应该有利于生物化学和医学以及化学工业的研究。