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DEVELOPMENT AND APPLICATIONS OF BISMUTH YLIDES AND BISMUTH IMIDES IN ORGANIC SYNTHESIS

叶立铋和酰亚胺铋的开发及其在有机合成中的应用

基本信息

批准号：
12640516
负责人：
MATANO Yoshihiro
金额：
$ 2.24万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

In this research project, I aimed to utilize the characteristics of hypervalent organobismuth compounds in organic synthesis and to develop new synthetic tools based on bismuth ylides (Ar_3Bi=CRR') and bismuth imides (Ar_3Bi=NR). (1) New methods for the synthesis of stabilized bismuth ylides and bismuth imides were established, and their structures and reactivities have been disclosed. Bismuth imides bearing an acyl or a sulfonyl group on the imido nitrogen atom were prepared by the metathesis reaction, and stabilized bismuth ylides were synthesized by the addition reaction of the imides with electron-deficient acetylenes. X-ray crystallographic analyses of these compounds have elucidated that the bismuth(V)-carbon and bismuth(V)-nitrodgen bonds possess a highly polarized, single bond character. Additionally, systematic comparisons of the structures of bismuth imides with those of the lighter 15th group element counterparts were made for the first time. (2) New cyclization methods by use of bismuth ylides and by bismuth imides have been developed. For instance, the reaction of alkynylbismuthonium salts with a suitable nucleophile generates bismuth ylides of the type Ar_3Bi=C=CRR', which subsequently undergo cyclization with elimination of triarylbisrnuthane to give cyclopentenes and 2,5-dihydrofurans. Stabilized bismuth ylides also undergo cyclization by heat or in the presence of a copper catalyst to afford oxazoles. The driving force of these transformations is the high leaving ability of the triarylbismuthonio group. (3) A new method for the selective synthesis of organobismuth compounds bearing a styryl group was established. They underwent radical polymerization to afford soluble polystyrenes bearing bismuth substitutes. (4) During the course of studies on the synthesis of bismuth imides, a new and convenient method for the preparation of bismuth oxides has been developed, and further studies on this class of compounds are now in progress.

在本研究项目中，我的目标是利用高价有机铋化合物在有机合成中的特性，开发基于铋叶立德（Ar_3Bi= CRR '）和铋酰亚胺（Ar_3Bi=NR）的新合成工具。(1)建立了稳定的铋叶立德和铋酰亚胺的合成新方法，并公开了它们的结构和反应性。通过复分解反应制备了亚氨基氮原子上带有酰基或磺酰基的铋酰亚胺，并通过酰亚胺与缺电子乙炔的加成反应合成了稳定的铋叶立德。这些化合物的X射线晶体学分析表明，铋（V）-碳和铋（V）-氮键具有高度极化的单键特征。此外，首次系统地比较了铋酰亚胺与轻的第15族元素对应物的结构。(2)发展了用叶立德和亚胺化铋进行环化的新方法。例如，炔基铋盐与合适的亲核试剂反应生成Ar_3Bi=C= CRR '型铋叶立德，其随后进行环化并消除三芳基双氨基甲烷，得到环戊烯和2，5-二氢呋喃。稳定的铋叶立德也通过加热或在铜催化剂存在下进行环化，得到恶唑。这些转变的驱动力是三芳基铋的高离去能力。(3)建立了一种选择性合成含苯乙烯基的有机铋化合物的新方法。他们进行自由基聚合，以提供可溶性聚苯乙烯轴承铋取代。(4)在研究铋酰亚胺的合成过程中，发展了一种新的简便的制备铋氧化物的方法，目前对这类化合物的进一步研究正在进行中。