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

考虑到过渡金属络合物，如钯和Ru，很容易使胺和醇脱氢生成金属氢化物中间体，开发了新型的催化氧化这些化合物的方法。典型结果总结如下1.以钨酸钠或二氧化硒为催化剂，过氧化氢催化氧化胺是一种制备相应硝酮的有效方法。这种方法也被发现用于将1，2，3，4-四氢喹啉转化为异羟肟酸。由于硝酮很容易转化为具有不同亲核性的-lt；α&gt；取代羟胺，因此研究了通过硝酮全合成具有生物活性的含氮分子，如鸟藤氨酸。在研究过程中，发现羟胺很容易通过使用钛…转化为胺或亚胺，这取决于所选择的反应条件更多的三氯化物。叔丁基氢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。Ru催化的醇的氧化通过脱氢过程提供酯。从反应的实际应用来看，香料中一些主要成分的酯是以醇为原料制备的，聚酯是由二元醇制备的。由于Ru催化的醇氧化反应在反应过程中产生了氢分子，因此已证明在相同的反应介质中，烯烃可以被氢化。研究了Ru催化叔丁基氢过氧化氢氧化氰醇生成酰基氰化物的反应。由此得到的酰基氰化物被用作多胺伯氨基的化学选择性酰化试剂。用这种方法建立了天然多胺如精胺和亚精胺生物碱的快速合成方法。较少

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