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

有机分子中氟的掺入改变了它们的化学和生物特性。许多可用的氟化剂是非特异性的和/或难以处理。解决这个问题的一个办法是使用含氟的小分子，这些小分子可以作为合成更复杂有机分子的基石。具体地说，将开发由共同前体α -氟- γ -取代烯基膦酸盐合成氟乙烯的新方法。该前体允许在α、β不饱和羰基化合物和共轭二烯醛中在烯烃碳上引入氟。在膦烯基酸盐上初始引入氟将使用一种众所周知的试剂，二乙胺硫三氟化（DAST）。所采用的方法将利用亲电性磷试剂作为将磷酸盐部分并入氟化乙烯前体的方法。这将导致磷周围有不同的取代基，这反过来又使对霍纳-沃兹沃思-埃蒙斯（HWE）缩合形成的氟烯烃获得更大的立体化学控制成为可能。有了这笔奖金，有机合成计划将支持马萨诸塞州达特茅斯大学的杰拉尔德·b·哈蒙德博士的研究。该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.