Development of New Synthetic Reactions Using Organosilicon Compounds

使用有机硅化合物开发新的合成反应

• 批准号: 14078205
• 负责人: HOSOMI Akira
• 金额: $ 18.18万
• 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 on Priority Areas
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14078205/
• 关键词: Organosilicon Reagents; Indium Catalyst; Reduction; Carbon-Carbon Bond Formation; Silyl Enolates; Aldol Reaction; ジメチルシリルエノラート; 立体選択的合成; タンデム反応; Mannich型反応; エナンチオ選択性; α-ジメチルシリルエステル; ケイ素反応剤; 不斉還元反応; Michael付加反応; 1,3-ジオール; α,β-不飽和カルボニル化合物

Most of organosilicon reagents have a trimethylsilyl (TMS) group or a more bulky triorganosilyl group. Synthetic utility of silicon reagents bearing a less bulky silyl group has remained unexplored. We have found that dimethylsilyl (DMS)-protected nucleophiles are more reactive than TMS-protected nucleophiles. For example, in the presence of CaCl_2, ketone DMS enolates added smoothly to aldehydes at 30℃ in DMF to give aldols in high yield. Under the same conditions, the corresponding TMS enolates did not react with aldehydes at all. In the reaction of DMS enolates, CaCl_2 would serve as Lewis base to activate the enolates by nucleophilic attack of the silicon by the chloride ion. DMS enolates are useful for the Mannich-type reaction of N-tosylimines and the Michael reaction of a-enones. Similarly, α-DMS-esters are more reactive than the corresponding TMS-based reagents. In the presence of metal chlorides (LiCl, MgCl_2, etc.), aldehydes and ketones underwent efficient aldol reactions of α-DMS-esters.In general, hydrosilanes do not react spontaneously with carbon electrophiles ; however, their reducing ability can be drawn by activation of the substrates or themselves. A proper choice of activator enables fine control of the reduction process. We have found that PhSiH_3 reacts with haloalkanes in the presence of In(OAc_3) to form the dehalogenated alkanes. This reduction would involve a radical chain mediated by indium hydride species. The PhSiH_3-In(OAc_3) system is applicable to intermolecular radical addition of haloalkanes to electron-deficient alkenes. Additionally, it is valuable also for reductive aldol reaction of a-enones with aldehydes. In this case, a plausible mechanism consists of ionic 1,4-reduction of a-enones with indium hydride species and aldol reaction of the resultant indium enolates.

大多数有机硅试剂具有三甲基酯（TMS）组或更笨重的三人组合，我们发现了二甲基（DMS）的二甲基（DMS）受到的二甲基溶液的补救措施在CACL_2的存在下，在同一分区下，DMF在DMF的30°C下平滑地烯醇化的醛。用氯离子作为硅的烯醇含量。试剂。在存在α-DMS酯的有效藻类反应的情况下，氢硅烷不会通过碳电力来自发地重新效果。可以对修订过程进行良好的控制。在电子固定烯烃中添加卤代的卤代烷基，在这种情况下，用于还原的A-烯烃。

项目成果

Regio and Stereoselective Homolytic Hydrostannylation of Propargyl Alcohols and Ethers with Dibutylchlorostannanes

炔丙醇和醚与二丁基氯锡烷的区域和立体选择性均裂氢甲锡烷基化

• 发表时间: 2003
• 期刊: The Journal of Organic Chemistry 68(22)
• 作者: Katsukiyo Miura;Akira Hosomi;A.Hosomi;A.Hosomi;杉浦 淳二;細見彰
• 通讯作者: 細見彰

混合反応剤及びそれを用いたアセタール類のアルキル化方法

混合反应物及使用其将缩醛烷基化的方法

• 发表时间: 2003

A.Hosomi: "Acid-Catalyzed Intramolecular Addition of a Carboxy Group to Vinylsilanes"J.Organometal.Chem. 686・21. 242-250 (2003)

A.Hosomi：“酸催化羧基与乙烯基硅烷的分子内加成”J.Organometal.Chem. 686・21（2003）。

A.Hosomi: "1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing an Amino Group"Chrality. 15・1. 41-52 (2003)

A.Hosomi：“带有氨基的乙烯基硅烷的1,2-甲硅烷基迁移环化”Chrality 15・1 (2003)。

Highly Regio- and Stereoselective Hydrostannylation of Propargyl Alcohols and Ethers Using Dibutylchlorostannane and Lithium Chloride and Lithium Chloride

使用二丁基氯锡烷和氯化锂对炔丙醇和醚进行高度区域和立体选择性氢化锡烷基化

• 发表时间: 2005
• 期刊: Synlett 3
• 作者: M.Okazaki;K.A.Jung;H.Tobita;A.Hosomi
• 通讯作者: A.Hosomi