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

在有机分子中掺入氟可以改变它们的化学和生物性质。许多可用的氟化剂都是非特异性的和/或太难处理。这个问题的一个解决方案是使用含氟的较小分子，这些分子可以在合成更复杂的有机分子时充当构建块的角色。具体地说，将开发从常见的前体α-氟-伽马取代的烯丙基膦酸酯合成乙烯基氟化物的新方法。这种前驱体将允许在α，β-不饱和羰基化合物和共轭双烯中的烯碳上引入氟。在丙烯基膦酸酯上的氟的初始引入将使用众所周知的试剂二乙氨基硫三氟化物(DAST)来完成。所采用的方法将利用亲电磷试剂作为一种方式将磷酸盐部分结合到氟乙烯前驱体中。这将在磷周围产生不同的取代基，从而使人们有可能对由Horner-Wadsworth-Emmons(HWE)缩合形成的氟烯烃进行更大的立体化学控制。有了这个奖项，有机合成计划将支持马萨诸塞大学达特茅斯分校的杰拉尔德·B·哈蒙德博士的研究。这项研究将探索在非腐蚀性条件下将氟引入复杂分子的新方法。这将有利于生物化学和医学以及化学工业的研究。

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.