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

在氮杂环上引入有用的功能碳取代基的方法学的发展对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，喹啉与氯甲酸苯酯和三氟甲磺酸银反应生成高活性的N-酰基喹啉鎓离子，N-酰基喹啉鎓离子与氯甲酸苯酯和三氟甲磺酸银反应生成高活性的N-酰基喹啉鎓离子，N-酰基喹啉鎓离子与氯甲酸苯酯和三氟甲磺酸银反应生成高活性的N-酰基喹啉鎓离子，N-酰基喹啉鎓离子与氯甲酸苯酯和三氟甲磺酸银反应生成高活性的N-酰基喹啉鎓离子，N-酰基喹啉鎓离子与氯甲酸苯酯和三氟甲磺酸银反应生成高活性的N-酰基喹啉鎓离子。由此产生的环烷基喹啉离子可以容易地与烯丙基硅烷反应。此外，还发现异喹啉与烯丙基硅烷的类似反应得到苯并异奎宁环体系。本年度的主要目的集中在改进反应条件以及借助于烯丙基硅烷以外的其它有机硅试剂的反应，以便将烯丙基以外的其它有用的碳取代基引入到氮杂芳族化合物中。官能团，例如酯基、甲酰基、氰基、 ...更多信息 在本反应中，杂芳环上的硝基是容许的，显示出高的化学选择性，尽管在某些情况下产率较低。通过实验发现，乙腈是比二氯甲烷更好的溶剂，几乎所有反应的产率都有所提高。这可能归因于在极性更强的乙腈溶液中有利于N-酰基喹啉离子的形成。从环境角度来看，使用非氯化溶剂是另一个优点。与2-甲基-、2-氯甲基-和2-三甲氧基-甲基烯丙基硅烷的反应也容易进行，以良好的产率得到加合物。β-咔啉体系的反应也进行得很好。其次，我们考察了它与联烯基、炔丙基和炔基硅烷的反应。已发现，在乙腈中等摩尔量的三氟甲磺酸银存在下，与丙二烯基硅烷的反应以良好的产率得到炔丙基化加合物。在催化量的三氟甲磺酸银存在下，与炔丙基硅烷的反应以良好的产率提供丙二烯基化加合物。此外，在等摩尔量的三氟甲磺酸银存在下，在高温下与反应性较低的炔基硅烷进行反应，以高产率得到炔基化加合物。少

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）。