A New Method for High Activation of Acyliminium Ions and Reactions with Group 14 Organometallic Reagents

酰亚胺离子高活化及其与14族有机金属试剂反应的新方法

• 批准号: 08455415
• 负责人: YAMAGUCHI Ryohei
• 金额: $ 4.42万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455415/
• 关键词: Group 14 Organometallic; Nitrogen Heteroaromatic; Acyliminum Ion; Allylsilane; Alkynylsilane; Allenylsilane; Quinolinium Ion; 銀トリフラート; 有機金属化合物

Development of methodology for introduction of useful functional carbon substituents into nitrogen heterocycles is of great importance of synthesis of various physiologically and pharmacolotically active nitrogen heterocyclic compounds.It has been found in the studies during 1996 that a highly activated N-acylquinolinium ion is generated when quinoline is treated with phenyl chloroformate and silver triflate and that N-ccylquinoliun ion thus pwoduced can readily react with allylsilanes. It has been found, furthermore, that the similar reaction of isoquinoline with allylsilane to the above affords a benzoisoquinuclidine system.On the basis of the above results, major purposes in this year are focused on improvements of the reaction conditions as well as the reactions by means of other organosilicon reagents than allylsilane in order to introduce other useful carbon substituents than allyl group into nitrogen heteroaromatics.A variety of functional groups, such as ester, formyl, cyano, a … More nd nitro, on heteroaromatics are tolerated in the present reaction, showing the high chemoselectivity, though the yields are low in some cases. After the through experiments, acetnitrile has been found to the better solvent than dichloromethane, increasing the yields in almost all of the reactions. This could be ascribed to a favorable formation of N-acyl-quinolinium ion in more polar acetonitrile solution. Use of non-chlorinated solvent is another advantage from environmental point of view. The reactions with 2-methyl-, 2-chloromethyl-, and 2-trimethysiloxy-methylallylsilanes also readily proceed to give adducts in good yields. The reactions of beta-carboline system also work very well.Next, the reactions with allenyl-, propargyl-, and alkynylsilanes have been examined. It has been found that the reactions with allenylsilanes in the presence of equimolar amount of silver triflate in acetnitrile gives propargylated adducts in good yields. The reactions with propargylsilanes in presence of catalytic amount of silver triflate afford allenylated adducts in good yields. Furthermore, the reactions with less reactive alkynylsilanes are conducted in the presence of equimolar amount of silver triflate at elevated temperature to give alkynylated adducts in goond yields. Less

开发在氮杂环中引入有用的功能性碳取代基的方法对于合成各种具有生理和药理活性的氮杂环化合物具有重要意义。1996年的研究发现，喹啉在合成时会产生高度活化的N-酰基喹啉鎓离子。用氯甲酸苯酯和三氟甲磺酸银处理，生成的N-环喹啉离子很容易与烯丙基硅烷反应。此外，还发现异喹啉与烯丙基硅烷的类似反应提供了苯并异奎宁环体系。基于上述结果，今年的主要目的集中在反应条件的改进以及通过其他方法进行反应。有机硅试剂比烯丙基硅烷，以便将除烯丙基之外的其他有用的碳取代基引入氮杂芳族化合物中。多种官能团，例如酯、甲酰基、氰基、杂芳烃上的硝基在本反应中具有较高的化学选择性，但在某些情况下收率较低。经过实验，发现乙腈是比二氯甲烷更好的溶剂，几乎提高了收率。这可能归因于在极性较大的乙腈溶液中有利地形成 N-酰基-喹啉鎓离子，这是使用非氯化溶剂的另一个优点。从环境角度来看，与 2-甲基-、2-氯甲基-和 2-三甲基甲硅烷氧基-甲基烯丙基硅烷的反应也很容易以良好的产率进行加合物。β-咔啉体系的反应也非常有效。已经检查了与丙二烯基硅烷、炔丙基硅烷和炔基硅烷的反应，发现在等摩尔量的银存在下与丙二烯基硅烷的反应。三氟甲磺酸银在乙腈中以良好的产率产生炔丙基化加合物，在催化量的三氟甲磺酸银存在下，与炔基硅烷的反应以良好的产率进行烯基化加合物。温度下以良好的产率得到炔基化加合物。

项目成果

山口 良平: "Triflate Ion-Promoted Addition Reaclion of Allylsilane to Quivolines and Isoquinolines Acylated by chloroformate Esters" Tetrahedron Letters. 38・3. 403-406 (1997)

Ryohei Yamaguchi：“三氟甲磺酸根离子促进的烯丙基硅烷与氯甲酸酯酰化的喹啉和异喹啉的加成反应”Tetrahedron Letters 38・3 (1997)。

山口 良平: "Triflate Ion-Prometed Addition Reaction of Allylsilane to Qumolines and Isoquinolines Acylated by Chloroformate Esters" Tetrahedron Letters. 38・3. 403-406 (1997)

Ryohei Yamaguchi：“氯甲酸酯酰化烯丙基硅烷与喹啉和异喹啉的三氟甲磺酸根离子促进加成反应”Tetrahedron Letters 38・3 (1997)。

Ryohei Yamaguchi: "Triflate Ion-Promoted Addition Reaction of Allylsilane to Quinolines and Isoquinolines Acyalted by Chloroformate Esters" Tetrahedron Lett.38-3. 403-406 (1997)

Ryohei Yamaguchi：“三氟甲磺酸根离子促进烯丙基硅烷与氯甲酸酯酰化的喹啉和异喹啉的加成反应”四面体 Lett.38-3。

山口 良平: "Triflate Ion Promoted Addition Reacting of Allylsilene to Quinelines and Isoquindines Acyleted by Chloroformate Esters" Tetrahedron Lett.38・3. 403-406 (1997)

Ryohei Yamaguchi：“三氟甲磺酸根离子促进烯丙基硅烷与氯甲酸酯酰化的奎因啉和异奎定的加成反应”Tetrahedron Lett.38・3（1997）。