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

在有机分子中掺入氟会改变它们的 化学和生物学特性。 许多可用的 氟化剂是非特异性的和/或太难 把手进行 这个问题的一个解决方案是使用 含氟的小分子， 在合成更复杂的有机分子中起关键作用。 特别是新的合成乙烯基氟从一个共同的 前体，α-氟-γ-取代的烯丙基膦酸酯， 将被开发。 这一先驱将允许引入 在α，β-不饱和的烯碳上的氟 羰基化合物和共轭二烯醛。 初始 将在烯丙基膦酸酯上引入氟 使用众所周知的试剂，二乙基氨基三氟化硫 （DAST）。 所采用的方法将利用亲电 磷试剂作为结合膦酸酯的方式 氟乙烯前体中的部分。 这将导致 磷周围有不同的取代基， 将使获得更大的立体化学控制成为可能 由Horner-Wadsworth-Emmons（HWE） 凝 %%% 有了这个奖项，有机合成计划将支持 Gerald B博士的研究。哈蒙德在牛津大学 马萨诸塞州，达特茅斯。 该研究将探讨 在配合物中引入氟的新方法的开发 分子在非腐蚀性条件下。 这应该有利于 生物化学和医学研究以及 化工专业化

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.