Novel Type of Catalytic Oxidations of Oxygen- and Nitrogen-Containing Organic Compounds

鉴于胺和醇很容易被过渡金属配合物如钯和钌脱氢生成金属氢化物中间体，开发了这些化合物的新型催化氧化方法。典型结果总结如下1。在钨酸钠或二氧化硒的催化下，用过氧化氢催化氧化胺已被证明是制备相应硝基酮的有效方法。该方法还可用于将1,2,3,4-四氢喹啉转化为羟肟酸。由于硝基酮很容易与各种亲核试剂转化为< α > -取代的羟胺，因此人们研究了通过硝基酮合成具有生物活性的含氮分子，如胆碱。在研究过程中发现，根据所选择的反应条件，羟胺可以很容易地转化为胺或亚胺。在钌配合物的催化下，叔丁基过氧化氢催化氧化仲胺也被证明是合成亚胺的一种有效方法。钌催化的醇氧化通过脱氢过程生成酯。从实际应用的角度出发，从醇类开始制备了一些香水中必需成分的酯类，从二醇开始制备了聚酯。由于钌催化醇的氧化在反应过程中产生氢分子，因此证明了烯烃在相同的反应介质中也能被氢化。研究了钌催化过氧化叔丁基氧化氰醇制酰基氰化物的工艺。所制得的酰基氰化物可作为多胺中伯胺基的化学选择性酰化试剂。用该方法可快速合成天然多胺，如精胺和亚精胺生物碱。少

In view of that amines and alcohols are readily dehydrogenated by transition metal complexes such as palladium and ruthenium to give metal hydride intermediates, novel types of catalytic oxidations of these compounds were developed. Typical results are summarized below.1. The catalytic oxidation of amines by hydrogen peroxide in the presence of sodium tungstate or selenium dioxide as the catalyst has proved to be a useful method for preparing the corresponding nitrones. This method has been also found to be useful for converting 1,2,3,4-tetrahydroquinolines into hydroxamic acids. Since nitrones are easily transformed into <alpha> -substituted hydroxylamines with various nucleophiles, the total synthesis of biologically active nitrogencontaining molecules, e.g. ochotensine, via nitrones has been investigated. During the course of this study hydroxylamines were found to be easily transformed into either amines or imines, depending on the reaction conditions chosen, by the use of titanium … More trichloride. The catalytic oxidation of secondary amines by tertbutyl hydroperoxide in the presence of ruthenium complexes as the catalyst has also proved to be a useful method for synthesizing imines.2. The ruthenium-catalyzed oxidation of alcohols provides esters via dehydrogenation processes. From the viewpoint of practical use of the reaction, some esters of essential components in perfumes were prepared starting from alcohols, and polyesters from diols. Since the ruthenium-catalyzed oxidation of alcohols produces hydrogen molecule during the course of the reaction, it has been demonstrated that olefins is able to be hydrogenated in the same reaction medium. The ruthenium-catalyzed oxidation of cyanohydrins with tert-butyl hydroperoxide leading to acyl cyanides was developed. The acyl cyanides thus obtained were found to be utilized as chemoselective acylating reagents of primary amino group of polyamines. A short-step synthesis of naturally occurring polyamines such as spermine and spermidine alkaloids has been established by using this method. Less