Studies on the Synthesis and the Application of New Functionalized Phosphines

在这个项目中，合成和新功能性磷酸酶的应用已经被研究，在第一章中，与铜至1，2-二（二<alpha><omega>苯基）环球系的氧化偶联，-磷基-稳定的二氯苯<Cl_2>基“甲基化数字对<alpha><omega>二磷氧化物对循环化的影响”已被证实。（ &lt;-_+&gt; ）-反式双-1，2-（二苯基）环丁烯（abbreviated DPCB氧化物）与L-（-）-二苯并基鞑靼酸（-）-DPCB氧化物减少为三聚氰胺，导致光学活性（+）-反式双-1，2-（diphenylphosphino）环丁烯（abbreviated DPCB）。反式DPCB的绝对配置是通过X射线分析对其镍复合物进行确定<Cl_2>的。通过一种新型的cationrhodium（I）复合体[Rh·（+）-DPCB·（1，5-COD）] &lt;^+BF_4^-&gt;成功地获得了所找到的氢化产品都很好（ca.）。90%）。一种新的生物配体， （2-氨基-1-磷酸）环烷烃已合成，在第二章，一种不同的试剂， （2-二氧磷酰环球）三苯醚磷酸盐已经开发出来。双重Wittig反应使用这种盐和各种碳基试剂在良好的年份中生产1，2-二（丁香）环球。1，2-之二（丁香）环球系未知的序列性炎症-Alder Reaction with 2 equiv。不同的二烯形态可以提供功能化的多环化合物。在合并中，这些结果可以说已经为这个项目完成了最初的专门主题。

In this project, the synthesis and the application of new functionalized phosphines were studied.In chapter 1, oxidative coupling of <alpha> , <omega> -phosphoryl-stabilized dicarbanions with Cu <Cl_2> led to 1,2-bis(diphenylphosphinyl)cyclobutanes. The effect of the methylene numbers of <alpha> , <omega> -diphosphine oxides on the cyclization was examined. The resolution of ( <-_+> )-trans-bis-1,2-(diphenylphosphinyl)cyclobutane (abbreviated DPCB oxide) with L-(-)-dibenzoyltartaric acid gave pure (-)-DPCB oxide, which was reduced with trichlorosilane to lead to optically active (+)-trans-bis-1,2-(diphenylphosphino)cyclobutane (abbreviated DPCB). The absolute configuration of trans-DPCB was determined by X-ray analysis of its Ni <Cl_2> complex. The asymmetric hydrogenation of dehydroamino acids catalyzed by a new type of cationic rhodium (I) complex [Rh・(+)-DPCB・(1,5-COD)] <^+BF_4^-> successfully gave the hydrogenated products whose optical yields were found to be good (ca. 90% ee). A new type of bidentate ligands, (2-amino-1-phosphino)cycloalkanes were synthesized.In chapter 2, a versatile reagent, (2-diethoxyphosphinylcyclobutyl)triphenylphosphonium salt was developed. The double Wittig reaction using this salt and various carbonyl reagents produced 1,2-bis(ylidene)cyclobutanes in good yields. The 1,2-bis(ylidene)cyclobutanes underwent sequential Diels-Alder reaction with two equiv. of various dienophiles to give functionalized polycyclic compounds.In conclusion, these results can be said to have achieved the initially attempted subjects for this project.