Synthesis and Application of Versatile Monofluoro Building Blocks by Manipulation of the Multifunctional Carbon Compounds.

鉴于最近对新材料和生物活性分子的兴趣和需求不断增加，尝试开发用于脂肪族单氟化合物的通用和实用的结构单元。我们的合成方法包括利用我们实验室最近开发的多官能碳化合物和方便的直接酯化法。研究结果如下：1.烷基化之后，选择性地将市售的硝基乙酸酯进行烷基化，产生2-氟-2-硝基烷酸酯（5），这是第一种含氟结构单元。1的有用性通过转化成各种单氟衍生物来证明。1的选择性酯化得到2-氟代烷酸酯（2）m，其进一步转化为相应的2-氟代烷酸和2-氟代烷醇。另一方面，1的脱烷氧羰基化得到氟硝基烷烃，其中引入第二个烷基以得到二烷基化的芴 ...更多信息 硝基甲烷（3）。3的取代反应成功地得到了含氟烷烃和含氟烯烃，它们的烷基链上只有一个氟原子，这取决于两个烷基的选择.尝试将第三烷基脱硝引入3中以产生叔烷基氟化物，尽管产率较低，这是各种有机氟化合物中最难制备的结构。另一方面，1的反式烷基化反应以高产率得到目标化合物。因此，我们已经开发了多功能的积木相当于一氟亚甲基二碳负离子的合成子。还从相应的双官能团碳化合物制备了1-苯磺酰基-1-氟-1-硝基烷烃（4）、2-苯磺酰基-2-氟链烷酸酯（5）和1-苯磺酰基-1-氟烃基膦酸酯（6）。去除4和5的官能团失败。然而，6与各种羰基化合物反应产生氟乙烯基砜衍生物（7）。再经michael加成、diels-alder反应、1，3-偶极环加成等反应生成各种单氟化合物。少

Development of versatile and practical building blocks for aliphatic monofluoro compounds was attempted in light of recent increasing interest and demand for both new materials and bioactive molecules. Our synthetic approach involves the utilization of the multifunctional carbon compounds and the convenient direct fluorination method which were recently developed in our laboratory. Results are summarized as follows;1. Alkylation follwed by selective fluorination of commercially available nitroacetates produced 2-fluoro-2-nitroalkanoic esters(5), the first fluorine-containing building blocks. The usefulness of 1 was demonstrated by converting into various monofluoro derivatives. Selective denitration of 1 gave 2-fluoroalkanoic esters(2)m which were further converted into the corresponding 2-fluoroalkanoic acids and 2-fluoroalkanols. On the other hand, dealkoxycarbonylation of 1 yielde fluoronitroalkanes, into which the second alkyl groups were introduced to give the di-alkylated fluoron … More itromethanes(3). denitration of 3 afforded successfully fluoroalkanes and fluoroalkenes, which have aingle fluorine atom on the alkyl chains dependent on the choice of teh two alkyl groups.2. Denitrative introduction of the third alkyl groups into 3 was attempted to produce the tertiary alkyl fluorides although in low yields, which are the most difficult structures to prepare among the various organofluorine compounds. On the other hand, denitrative alkylation of 1 gave the target compounds in high yields. We have thus developed versatile building blocks equivalent to the synthon of monofluoromethylene dicarbanion.3. 1-Benzenesulfonyl-1-fluoro-1-nitroalkanes(4), 2-benzenesulfonyl-2-fluoroalkanoic esters(5), and 1-benzenesulfonyl-1-fluorophoalkylphosphonates(6) were also prepared from the corresponding difunctional carbon compounds. Removal of the functional groups of 4 and 5 failed. However, reaction of 6 with various carbonyl compounds produced fluorovinylsulfone derivatives(7). Which were further transformed into various monofluoro compounds via michael addition, diels-alder reaction, and 1,3-dipolar cycloaddition. Less