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Creation of Highly Functional Reagents and its Application to Novel Organic Synthesis

高功能试剂的创建及其在新型有机合成中的应用

基本信息

批准号：
07555276
负责人：
HOSOMI Akira
金额：
$ 6.21万
依托单位：
University of Tsukuba
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

项目摘要

The following results are obtained in this research project.1.Manganese Ate Complexes as a New Reducing Agent : Perfectly Regiocontrolled Generation and Reactions of the Mn-Enolates with ElectrophilesManganese (II) ate complexes cleanly react with carbonyl compounds bearing a leaving group at the alpha position to generate the enolates of the original ketones, esters, and amides, irrespective of their structure, where the manganate serves as a reductant not an alkylation agent. In this reductive generation of the enolates based on the novel reactivity of the manganese ate complexes, a kind of oxidative addition of a substrate to the ate complex and the reductive elimination of the ligands on manganese are possibly involved as the key processes, while the process equivalent to "metal-halogen exchange" does not seem to be significant. The generality of this reaction was demonstrated in the generation of the enolates of not only aromatic ketones and aliphatic ketones but also an aliphatic … More ester and amide. As for the synthetic value, this reaction was successfully applied to the perfectly regiospecific generation and reactions of a pair of the regioisomeric enolates corresponding to the unsymmetrical and non-branched aliphatic ketones.2.Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsSamarium reveals a strong reducing ability and by virtue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, non-stabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.3.Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an AcidThe acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyrans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion. Less

本课题主要取得了以下研究成果：1.新型还原剂--锰原子络合物：Mn-烯醇化物与亲电体的完美区域控制的生成和反应锰（II）配合物与在α位带有离去基团的羰基化合物干净地反应，生成原始酮、酯和酰胺的烯醇化物，而不管它们的结构如何，其中所述烷基化剂用作还原剂而不是烷基化剂。在这种基于锰酸盐络合物的新颖反应性的烯醇化物的还原生成中，可能涉及一种底物对酸盐络合物的氧化加成和锰上配体的还原消除作为关键过程，而相当于“金属-卤素交换”的过程似乎并不重要。该反应的一般性不仅表现在芳香酮和脂肪酮的烯醇化物的生成上，而且表现在脂肪酮的烯醇化物的生成上。 ...更多信息酯和酰胺。就合成价值而言，该反应成功地应用于一对对应于不对称非支链脂肪酮的区域异构烯醇化物的完美区域专一性生成和反应。2.前所未有的钐介导反应：非稳定羰基叶立德的产生钐显示出强还原能力，并且凭借这种特性连同其亲氧性，广泛应用于有机合成中碳-碳键的形成和各种官能团的高选择性转化。在我们对反应物种的产生和反应的研究过程中，本文报道了由钐介导的碘甲基硅醚产生的新的活性物种，非稳定的羰基叶立德，以及它们与各种不饱和化合物如醛，烯烃，联烯，3.通过酸催化的带有羟基的乙烯基硅烷的硅导向环化带有羟基的乙烯基硅烷的酸催化环化干净地进行以得到四氢呋喃和四氢吡喃，羟基与乙烯基硅烷的加成以顺式立体选择性方式进行。少