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.含二甲基硅基的合成试剂及其应用研究在碱金属或碱土金属盐存在下，二甲基硅基烯醇化物与醛的羟醛缩合反应可以有效地进行。作为使用各种金属盐的反应的结果，发现金属氯化物显示出高活性，并且反应机理涉及甲硅烷基烯醇化物的亲核活化。有趣的是，羟醛缩合反应甚至在水的存在下进行，并且甲醛的水溶液是可用的。在氯化镁存在下，DMS烯醇化物与α-mopes反应，以良好至高产率得到Michael加成物。在类似条件下，DMS烯醇化物也添加到N-甲苯磺酰亚胺中。水和催化量的二异丙胺的组合使用有效地诱导了曼尼希型反应。碱催化的Mannich型反应显示出高水平的非对映选择性。碱金属或碱土金属盐能有效地促进α-DMS酯与醛、酮的羟醛缩合反应。与α-烯酮的反应优先得到羟醛加合物而不是Michael加合物。发现DMS醚和DMS胺在刘易斯酸催化的羰基化合物的还原醚化和胺化中是有效的2。在催化量的乙酸铟（III）存在下，烷基卤与苯基硅烷发生还原反应，以高产率得到烷烃。这种还原耐受极性官能团，如醚和酯基团。反应机理可能涉及自由基还原与氢化铟物种生成的乙酸铟（III）和苯基硅烷。该还原体系适用于卤代烷与缺电子烯烃的分子间自由基加成反应

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: "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: "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: "Main Group Metals in Organic Synthesis"Wiley-VCH, Weinheim, Germany (in press). 183 (2004)

Katsukiyo Miura：“有机合成中的主族金属”Wiley-VCH，Weinheim，德国（印刷中）。