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

鉴于胺和醇容易被过渡金属络合物如钯和钌脱氢而得到金属氢化物中间体，开发了这些化合物的新型催化氧化。典型结果总结如下。以钨酸钠或二氧化硒为催化剂，过氧化氢催化氧化胺类化合物是一种制备硝酮的有效方法。还发现该方法可用于将1，2，3，4-四氢喹啉转化为异羟肟酸。由于硝酮很容易<alpha>被各种亲核试剂转化为β-取代的羟胺，因此研究了通过硝酮全合成具有生物活性的含氮分子，例如ochotensine。在本研究过程中，发现通过使用钛，根据所选择的反应条件，羟胺容易转化为胺或亚胺 ...更多信息 - 是的在钌配合物催化下，叔丁基过氧化氢催化氧化仲胺也被证明是一种合成亚胺的有效方法.醇的季铵盐催化氧化通过脱氢过程提供酯。从反应的实际应用角度出发，一些香料中必需成分的酯是由醇类开始制备的，而聚酯是由二元醇类开始制备的。由于醇的铼催化氧化在反应过程中产生氢分子，因此已经证明烯烃能够在相同的反应介质中氢化。研究了季铵盐催化叔丁基过氧化氢氧化氰醇生成酰基氰的反应。由此获得的酰基氰化物被发现可用作多胺伯氨基的化学选择性酰化试剂。用此方法建立了天然多胺如精胺和亚精胺生物碱的一种短步骤合成方法。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