Development of New Synthetic Reactions Using High Efficient Acidic Catalysts

使用高效酸性催化剂开发新的合成反应

• 批准号: 04453029
• 负责人: MUKAIYAMA Teruaki
• 金额: $ 4.61万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453029/
• 关键词: Acidic catalyst; Carboxylic ester; Glycosylation; 1,2-Cis glycoside; 2-Amino sugar; Ribose; Arabinose; 触媒的フリーデルクラフツ反応; 触媒反応; エステル化; チオエステル; 芳香族ケトン; 対イオン

In this research, new synthetic reactions using acitive acidic catalysts have been developed By using these novel catalysts, high efficiency has been attained.1. In the presence of a catalytic amount of TiCl_4 and a stoichiometric amount of p-trifluoromethylbenzoic anhydride, aniline reacted with carboxylic acid trimethylsilylesters to give the corresponding carboxylic anilides in high yields.2. In the presence of an active catalyst prepared from SiCl_4 and AgClO_4 and a stoichiometric amount of p-trifluoromethylbenzoic anhydride, carboxylic acids or their trimethylsilyl esters reacted with aromatic compounds to afford the corresponding Friedel-Crafts adducts in high yields.3. In the presence of a catalytic amount of trityl salt, epoxides reacted with silylated nucleophiles to give the adducts, via carbon-carbon and carbon-oxygen bonds formation and rearrangement.4. Several stereoselective glycosylation reactions of 2-amino sugars, arabinose, ribose, etc. were developed by using active catalysts under mild conditions.

在本研究中，开发了新型的酸性催化剂合成反应。使用这些新型催化剂，已经实现了高效率。在催化量的TiCl_4和化学计量的对三氟甲基苯甲酸酐存在下，苯胺与羧酸三甲基硅酯反应，高产率地得到了相应的羧酰苯胺.在SiCl_4和AgClO_4制得的活性催化剂和化学计量的对三氟甲基苯甲酸酐存在下，羧酸或其三甲基硅酯与芳香族化合物反应，高产率地得到相应的Friedel-Crafts加成物.在催化量的三苯甲基盐存在下，环氧化物与硅烷化亲核试剂反应，通过碳-碳键和碳-氧键的形成和重排得到加合物.利用活性催化剂，在温和的条件下，开展了2-氨基糖、阿拉伯糖、核糖等的几种立体选择性糖基化反应。

项目成果

T.Mukaiyama: "Catalytic Stereoselective Synthesis of α-orβ-Ribofuranosides by Combined Use of Silver Salts and Lithium Perchlorate" Chemistry Letters. 1993. 781-784 (1993)

T.Mukaiyama：“联合使用银盐和高氯酸锂催化立体选择性合成 α-或β-呋喃核苷”化学快报 1993 年。781-784 (1993)

M.Miyashita: "A Convenient Synthesis of Corboxanilides from Silyl Carboxylates and Weakly Nudeophilic Anilines Using p-Trifluoromethylbenzoic Anhydride" Bull.Chem.Soc.Jpn.67. 210-215 (1994)

M.Miyashita：“使用对三氟甲基苯甲酸酐从甲硅烷基羧酸酯和弱亲核苯胺方便地合成 Corboxanilides”Bull.Chem.Soc.Jpn.67。

T.Mukaiyama: "Catalytic Stereoselective Synthesis of alpha- or beta- Ribofuranosides by Combined Use of Silver Salts and Lithium Perchlorate of Diphenyltin Sulfide" Chemistry Letters. 1993. 781-784 (1993)

T.Mukaiyama：“结合使用二苯基锡硫化物的银盐和高氯酸锂催化立体选择性合成 α- 或 β- 呋喃核糖苷”。

I.Shiina: "A Useful Method for the Preparation of Carboxylic Esters from Free Carboxylic Acids and Alcohols" Chemisty Letters. 1994. 515-518 (1994)

I.Shiina：“从游离羧酸和醇制备羧酸酯的有用方法”化学快报。

K.Suzuki: "The Catalytic Friedel‐Crafts Acylation Reaction Starting from Aromatic Compounds and Free Carboxylic Acids(or their Trimethylsilyl Esters)by Promotion of Silicon(IV)Cationic Species" Bull.Chem.Soc.Jpn.66. 3729-3734 (1993)

K.Suzuki：“通过促进硅 (IV) 阳离子物种，从芳香族化合物和游离羧酸（或其三甲基甲硅烷基酯）开始催化弗里德尔-克来福特酰化反应”Bull.Chem.Soc.Jpn.66（ 1993）