Development of new synthetic method based on the substitution on the nitrogen atom oximes

1)芳香族化合物的直接胺化反应。在SnCl4和CF3SO3H存在下，富电子芳香族化合物与1-吲酮-0-甲磺酰肟反应生成相应的亚胺。2)二氢吡咯和四氢吡啶的制备2)二氢吡咯和四氢吡啶的制备在DBU的存在下，具有活泼亚甲基的酮0-甲磺酰肟在DBU的存在下进行分子内取代反应，分别得到3，4-二氢-2H-吡咯或2，3，4，5-四氢吡啶。3)有机金属与邻磺基衍生物偶联反应制备伯胺。也就是说，在CuCN作为催化剂…存在的情况下更多的t，烷基格氏试剂与4，4‘-双(三氟甲基)二苯甲酮反应生成N-烷基亚胺，N-烷基亚胺的水解高产率地生成伯烷基胺、仲烷基胺和叔烷基胺。通过使用3，3‘，5，5’-四(三氟甲基)二苯甲酮0-对甲苯磺胺，在没有铜催化剂的情况下与格氏试剂进行反应，所得亚胺经水解得到苯胺和烷基胺。4)通过亚烷氨基基制备含氮杂环化合物间羟基苯乙酮0-2，4-二硝基苯肟经NaH和DDQ处理后在分子内环化，得到8-羟基喹啉。间羟基苯乙酮0-2，4-二硝基苯肟与NaH和NaBH_3CN反应生成8-羟基-四氢喹啉。研究发现，这些反应是通过两个苯基之间的一个电子转移生成的亚烷氨基基中间体进行的。这种产生亚烷氨基基的电子转移方法被进一步用于通过分子内自由基加成到烯烃部分来合成3，4-二氢-2H-吡咯衍生物。较少

New synthetic methods have been developed for the synthesis of various amino compounds based on the substitution reaction on the sp2 nitrogen atom of oximes.1) Preparation of anilines by the direct amination of aromatic compoundsElectron rich aromatic compounds react with 1-indanone 0-methylsulfonyloxime in the presence of SnCl_4 and CF_3SO_3H,giving the corresponding imines. The imines thus formed are converted to aniline derivative by hydrolysis.2) Preparation of dihydro pyrroles and tetrahydropyridinesIntramolecular substitution reaction of ketone 0-methylsulfonyloxime having active methylene group at the gamma- or delta-position proceeds in the presence of DBU to afford 3,4-dihydro-2H-pyrrole or 2,3,4,5-tetrahydropyridine, respectively.3) Preparation of primary amines by coupling reactions of organometallics with 0-sulfonyloximesPrimary amines are synthesized by the coupling reaction between organometallic reagents and 0-sulfonyloximes. That is, in the presence of CuCN as a catalys … More t, alkyl Grignard reagents react with 4,4'-bis (trifluoromethyl) benzophenone to give N-alkylimines, the hydrolysis of which yields primaray, secondary, and tertiary-alkylamines in high yield. By employing 3,3', 5,5'-tetrakis-(trifluoromethyl) benzophenone 0-p-toluenesulfonyloxime, the reaction with Grignard reagents proceeds without the copper catalyst, and anilines and alkylamines are obtained after hydrolysis of the resulted imines.4) Preparation of the nitrogen containing heterocyclic compounds via alkylideneaminyl radicalsIntramolecular cyclization of m-hydroxyphenethylketone 0-2,4-dinitrophenyloximes proceeds by the treatment with NaH and DDQ,affording 8-hydroxyquinolines. The reaction of m-hydroxyphenethylketone 0-2,4-dinitrophenyloximes with NaH and NaBH_3CN gives 8-hydroxy-tetrahydroquinolines. It was found that these reactions proceed via an alkylideneaminyl radical intermediate generated by one electron transfer between the two phenyl groups. This electron transfer method for the generation of alkylideneaminyl radicals is further utilized for the synthesis of 3,4-dihydro-2H-pyrrole derivatives by the intramolecular radical addition to an olefinic moiety. Less