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New Synthetic Methods of Aromatic and Heterocyclic Compounds

芳香族及杂环化合物的合成新方法

基本信息

批准号：
10440213
负责人：
NARASAKA Koichi
金额：
$ 8.26万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

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.

本文综述了肟衍生物作为亲电胺化试剂在杂环化合物合成中的应用。虽然肟衍生物通常会发生Beckmann重排反应，但当具有适当离去基团的肟与亲核试剂反应时，发现在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。肟是格氏试剂制备伯胺的亲电胺化试剂。此外，还发现O-2，4-二硝基苯肟通过单电子还原生成亚烷基胺基自由基。该方法可应用于喹啉、吡咯、咔啉等杂环化合物的合成。利用这种肟的自由基环化反应，实现了吡咯里西啶生物碱-异长春碱的全合成。此外，发现O-五氟苯甲酰肟发生氧化加成到Pd（0）络合物，生成亚烷基氨基钯物种。实现了不饱和酮O-五氟苯甲氧肟在钯（0）催化下转化为吡咯、吡啶、异喹啉和氮杂奥林等化合物。在芳香族化合物的合成中，间位取代芳香族化合物的制备是重要问题之一。通过环己二烯酮-铁羰基络合物与高级铜酸盐反应，区域选择性地合成了间酰基苯胺、苯酚、烷基苯衍生物。

项目成果

期刊论文数量（46）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

奈良坂紘一他3名: "Regioselective Acylation of (5-Alkylidene-1,3-cyclohexadiene)tricarbonyliron Complexes by the Reaction with Organometallic Reagents." Chemistry Letters. 395-396 (1998)

Koichi Narasaka 和其他 3 人：“通过与有机金属试剂的反应实现（5-亚烷基-1,3-环己二烯）三羰基铁配合物的区域选择性酰化”（Regioselective Acylization of (5-Alkylidene-1,3-cyclohexadiene) tricarbonyiron Complexes by the Reaction with OrganicMetalic Reagents）。