New Aspect on the Chemistry of Allenes

艾伦化学的新观点

基本信息

批准号：
16390005
负责人：
MUKAI Chisato
金额：
$ 9.54万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

This program has been directed toward development of efficient and novel reactions based on the inherent property of allenes, in particular, the allene possessing an electron-withdrawing group such as a phenylsulfonyl group. As a result, the following several reactions could be developed.(1) Treatment of 1-phenylsulfonylallene with a proper (co-hydroxy) alkyl side chain at the C,-position with a base afforded the corresponding oxacycles through the endo-mode cyclization process. This novel ring-closing reaction could be applied for the construction of five-to nine-membered oxacycles. The aza-congeners as well as carbocycles were also found to be prepared according to the standard conditions, thus developed. The sulfoxide, phosphine oxide, phosphonate, and ester functionalities were used as an electron-withdrawing group instead a sulfonyl moiety. Furthermore, allenylaniline derivatives provided the corresponding 2,3-disubstituted indoles in an endo-mode ring-closing manner. The allenyla … More niline having a hydroxymethyl group was converted into the indole-2,3-quinodimethane derivative via the intramolecular SN2' reaction.(2) The Pauson-Khand reaction of allenynes in the presence of Rh catalyst resulted in the efficient formation of bicyclo[4.3.0] as well as bicyclo[5.3.0] skeletons, the latter of which could not be prepared by the Pauson-Khand reaction of enynes. This new-type of Pauson-Khand reaction furnished the bicyclo[6.3.0] framswork as well. Alternatively, the carbodlimide functionality, which is isoelectronic to the allene group, could be successfully used in the Pauson-Khand reaction leading to the efficient construction of pyrrolo[2,3-b]indo1-2-ones.(3) Reaction of ene-bisallenes, generated from the corresponding propargyl alcohols, underwent the 6π-electrocyclic reaction to afford the quinodimethanes, which were susceptible to the [4+2]cycloaddition reaction with dienophiles. This novel method for the generation of quinodimethane species could be applied for the production of the naphthoquinodimethanes from benzene-bridged bisallene. Interestingly enough, the proper choice of the conditions in the step of bis-allene formation produced the cyclobutene derivatives instead of the [4+2]cycloadducts even if the suitable dienophiles were in existence. Less

该程序已针对基于艾伦的继承特性，特别是具有苯基磺酰基群等电子的艾琳（Allene）的继承性质的发展。结果，可以开发以下几种反应。（1）在C处使用适当的（羟基）烷基侧链处理1-苯基磺酰基，并通过碱基通过内摩德式环化过程为相应的Oxacycles提供。这种新型的闭环反应可用于构建五到九元的牛体。还发现根据标准条件制备AZA-CONGERS和碳循环。磺代，氧化磷，膦酸酯和酯功能被用作吸电子基团而代替磺酰基部分。此外，艾烯基苯胺衍生物以闭合环插曲的方式提供了相应的2,3二取代的吲哚。甲烯基…具有羟基甲基的更多二利氨酸通过分子内SN2'反应转化为2,3-二甲烷衍生物。（2）艾伦尼斯的pauson-khand反应在RH催化作用的情况下，在有效的Bicyclo [4.3.0] and Bycyclos and Bycycly [4. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3. 0. 3.由Enynes的Pauson-Khand反应制备。 Pauson-Khand反应的这种新型型也提供了Bicyclo [6.3.0]框架。 Alternatively, the carbon dioxide functionality, which is isoelectronic to the allene group, could be successfully used in the Pauson-Khand reaction leading to the efficient construction of pyrrolo[2,3-b]indo1-2-ones.(3) Reaction of ene-bisallenes, generated from the corresponding propargyl alcohols, underwent the 6π-electrocyclic reaction to afford the Quinodimethanes,这容易受到[4+2]的环加成反应的影响。这种新的喹硫非胺物种产生的方法可用于从苯桥接的双甲烯基生产萘喹啉甲烷。有趣的是，即使存在合适的Dinophiles，在双抗烯烯型形成步骤中的适当选择也会产生细胞周期烯衍生物，而不是[4+2] CycloadDucts。较少的