New Synthetic Methods of Aromatic and Heterocyclic Compounds

以肟衍生物为亲电胺化试剂合成杂环化合物，研究了各种胺化反应的发展。尽管肟衍生物一般进行Beckmann重排，但研究发现，当具有适当离开基团的肟用亲核试剂处理时，在sp2肟氮上进行的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。在制备伯胺的格氏试剂中，肟类化合物被发现是亲电胺化试剂。此外，还发现O-2，4-二硝基苯肟通过单电子还原生成烷基氨基基物种。该工艺可用于合成多种杂环化合物，如喹啉、吡咯、咔啉衍生物等。应用这一自由基环化反应，实现了吡咯里西丁生物碱的全合成。此外，还发现O-五氟苯甲酮与Pd(0)发生氧化加成反应，生成亚烷基胺基钯物种。这实现了Pd(0)催化不饱和酮O-五氟苯并肟转化为吡咯、吡啶、异喹啉和偶氮唑烯。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。以环己二酮-铁羰基络合物为原料，与高阶铜酸盐反应，区域选择性地合成了间酰基苯胺、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.