New Synthetic Methods of Aromatic and Heterocyclic Compounds

以肟类衍生物为亲电胺化试剂，研究了各种胺化反应的发展。虽然肟类衍生物通常发生贝克曼重排，但发现当具有适当离去基的肟类与亲核试剂处理时，sp^2肟氮上发生s_n2型反应。通过分子内反应合成了各种环亚胺和喹啉类化合物。发现氧肟是格氏试剂制备伯胺的亲电胺化试剂。此外，还发现o -2,4-二硝基苯基肟通过单电子还原形成烷基基胺基自由基。该方法可用于合成各种杂环化合物，如喹啉、吡咯和羰基衍生物。利用肟的这种自由基环化反应，实现了吡咯利西啶类生物碱的全合成。此外，Pd(0)配合物发生o -五氟苯甲酰肟的氧化加成反应，生成烷基烯酰胺类钯。这实现了不饱和酮o -五氟苯甲酰肟在Pd(0)催化下转化为吡咯、吡啶、异喹啉和氮唑烯。在芳香族化合物的合成中，m取代芳香族化合物的制备是一个重要的问题。采用环己二烯-羰基铁配合物与高阶铜酸盐进行区域选择性反应，制备了间酰基苯胺、苯酚、烷基苯衍生物。

Development of various amination reactions has been studied by using oxime derivatives as electrophilic aminating reagents toward the synthesis of heterocycles. Although oxime derivatives generally undergo the Beckmann rearrangement, it was found that S_N2-type reaction on the sp^2 oxime nitrogen proceeds when the oxime having proper leaving group is treated with nucleophile. Various cyclic imines and quinolines are synthesized by the intramolecular reactions. Oximes are found to be the electrophilic aminating reagent for the Grignard reagent to prepare primary amines. Moreover, it was found alkylideneaminylradical species are formed from O-2,4-dinitrophenyloximes by one-electron reduction. This process can be applied to the synthesis of various heterocycles, such as quinolinol, pyrrole and carboline derivatives. Total synthesis of a pyrrolizidine alkaloid, xenovenine, was achieved by applying this radical cyclization reaction of the oxime. Furthermore, it was found that oxidative addition of O-pentafluorobenzoyloximes occurs to Pd (0) complexes, generating alkylideneamidopalladium species. This realized the Pd(0)-catalized transformation of unsaturated ketone O-pentafluorobenzoyloximes to pyrroles, pyridines, isoquinolines and azaazulenes.On synthesis of aromatic compounds, preparation of m-substituted aromatic compounds is one of the important issue. m-Acyl aniline, phenol, alkylbenzene derivatives were prepared regioselectively by the reaction of cyclohexadienone-iron carbonyl complex and higher order cuprate.