Development of New Organosiiicon Reagents and Its Application to Environmentally Benign Organic Synthesis

新型有机试剂的研制及其在环保有机合成中的应用

• 批准号: 13650910
• 负责人: MIURA Katsukiyo
• 金额: $ 2.62万
• 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 (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650910/
• 关键词: Dimethylsilyl Enolate; α-Dimethylsilylester; Aldol Reaction; Michael Addition; Mannich Reaction; Indium; Radical Reduction; Radical Addition; ヒドロシラン; タンデム反応

1. Development of Synthetic Reagents Bearing a Dimethylsilyl Group and Its ApplicationThe aldol reaction of dimethylsilyl (DMS) enolates with aldehydes proceeded efficiently in the presence of alkali or alkali earth metal salts. As the result of reactions using various metal salts, it was found that metal chlorides show high activity and the reaction mechanism involves nucleophilic activation of silyl enolates. Interestingly, the aldol reaction proceeded even in the presence of water, and an aqueous solution of formaldehyde was usable. In the presence of magnesium chloride, DMS enolates reacted with α-mopes to give Michael adducts in good to high yields. Under similar conditions, DMS enolates also added to N-tosylimines. The Mannich-type reaction was effectively induced by the combined use of water and a catalytic amount of diisopropylamine. The base-catalyzed Mannich-type reaction showed high levels of diastereoselectivity. The aldol reactions of α-DMS-esters with aldehydes and ketones were effectively accelerated by alkali or alkali earth metal salts. The reaction with α-enones afforded aldol adducts in preference to Michael adducts. DMS ethers and DMS amines were found to be effective in the Lewis acid-catalyzed reductive etherification and amination of carbonyl compounds2. Radical Reactions Using Indium Catalysts and HydrosilanesIn the presence of a catalytic amount of indium(III) acetate, alkyl halides underwent reduction with phenylsilane to give alkanes in good yield. This reduction is tolerant to polar functionalities such as ether and ester groups. The reaction mechanism probably involves radical reduction with indium hydride species generated from indium(III) acetate and phenylsilane. The reduction system was applicable to an efficient intermolecular radical addition of alkyl halides to electron-deficient alkenes

1.带有二甲基甲硅烷基的合成试剂的开发及其应用二甲基甲硅烷基(DMS)烯醇化物与醛的羟醛反应在碱金属或碱土金属盐的存在下有效地进行。使用各种金属盐的反应结果发现：金属氯化物表现出高活性，反应机理涉及硅基烯醇化物的亲核活化。在氯化镁存在下，可以使用 DMS 烯醇化物与 α-mopes 反应，以良好至高的产率生成迈克尔加合物。结合使用水和催化量的二异丙胺可有效引发碱催化的曼尼希型反应。碱金属或碱土金属盐可有效加速 α-DMS 酯与醛和酮的羟醛反应。与 α-烯酮的反应优先于 DMS 醚和 DMS 胺生成羟醛加合物。在使用铟催化剂的路易斯酸催化的羰基化合物的还原醚化和胺化反应中有效。氢硅烷在催化量的乙酸铟(III)存在下，卤代烷与苯基硅烷进行还原，以良好的收率得到烷烃。这种还原反应能够耐受极性官能团，例如醚和酯基团。反应机理可能涉及自由基还原。由乙酸铟(III)和苯基硅烷生成的氢化铟物种该还原体系适用于有效的分子间自由基加成。卤代烷转化为缺电子烯烃

项目成果

三浦勝清: "Stereoselective Synthesis of Substituted Cyclic Ethers and Amines by Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy or Amino Group"Synlett. 2号. 143-155 (2003)

Katsukiyo Miura：“通过酸催化环化带有羟基或氨基的乙烯基硅烷来立体选择性合成取代的环状醚和胺”Synlett，No. 2. 143-155 (2003)。

三浦勝清: "1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing an Amino Group"Chirality. 15巻・1号. 41-52 (2003)

Katsukiyo Miura：“带有氨基的乙烯基硅烷的 1,2-甲硅烷基迁移环化”手性，第 15 卷，第 1. 41-52 期（2003 年）。

三浦 勝清: "Lewis Base-Promoted Aldol Reaction of Dimethylsilyl Enolates in Aqueous Dimerhylformamide : Use of Calcium Chloride as a Lewis Base Catalyst"Journal of the American Chemical Society. 124号4巻. 536-537 (2002)

Katsukiyo Miura：“二甲基甲硅烷基烯醇化物在水性二聚甲酰胺中的路易斯碱促进的羟醛反应：使用氯化钙作为路易斯碱催化剂”美国化学会杂志 124 第 4 期。536-537 (2002)。

三浦勝清: "Magnesium Chloride-Promoted Michael Addition of Dimethylsilyl Enolates to α-Enones"Synlett. 13号. 2068-2070 (2003)

Katsukiyo Miura：“氯化镁促进二甲基甲硅烷基烯醇化物与 α-烯酮的迈克尔加成”Synlett，第 13 号。2068-2070 (2003)

三浦 勝清: "Lewis Base-Promoted Aldol Reaction of Dimethylsilyl Enolates in Aqueous Dimethylformamide : Use of Calcium Chloride as a Lewis Base Catalyst"Journal of the American Chemical Society. 124巻4号. 536-537 (2002)

Katsukiyo Miura：“二甲基甲酰胺水溶液中二甲基甲硅烷基烯醇化物的路易斯碱促进的羟醛反应：使用氯化钙作为路易斯碱催化剂”美国化学会杂志，第 124 卷，第 4 期，第 536-537 期（2002 年）。