New Syntheses of Highly Reactive and Functional Organometallic Compounds and its Application to Organic Syntheses

高活性、功能性有机金属化合物的新合成及其在有机合成中的应用

• 批准号: 13450362
• 负责人: HOSOMI Akira
• 金额: $ 9.66万
• 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 (B)
• 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/en/grant/KAKENHI-PROJECT-13450362/
• 关键词: Si-Cu exchange reaction; Copper(I) Salt; Conjugate Silylation; Boration; Pd catalysts; Catalytic Reaction; Disilane; Gold(I) Complexes; 非局在電子系分子; ケイ素-銅交換反応

The following results are obtained in this research project1.New Reactivity of a Reducing Reagent Generated from a Copper(I) Salt and a Hydrosilane : Selective Reduction of Ketones and Olefins Conjugated with an Aromatic GroupAromatic ketones and olefins were selectively converted to the corresponding alcohols and alkanes by a reagent prepared from a copper(I) salt and a hydrosilane. Excess use of the hydrosilane is most important to attain the high reactivities. One-electron transfer process as well as nucleophilic reaction of hydride would contribute the selectivity2.First Gold Complex-catalysed Selective Hydrosilylation of Organic CompoundsThe first example of the hydrosilylation of organic compounds such as aldehydes and an aldimine using a catalytic amount of a gold complex, which accomplished versatile regio-and chemoselective reduction of carbonyl compounds, is described3.Convenient Methods for Conjugate Silylation of α,β-Enones Using a Disilane Mediated by a Copper(I) SaltThe β … More -Silylation of α,β-enones using disilanes smoothly proceeds with a stoichiometric and catalytic amount of a readily available copper(I) salt by easy manipulation. At elevated temperature, a stoichiometric amount of CuCl is effective for the silylation. In the presence of a silyl triflate, use of a catalytic amount of Cu_2O affords the product even at lower temperature. These procedures offer convenient tools for the synthesis of b-silylated ketones.4.New Method for Introduction of a Silyl Group into α,β-Enones Using a Disilane Catalyzed by a Copper(I) SaltThis paper describes that the reaction of a disilane with a Cu(I) salt efficiently induces cleavage of the Si-Si bond cc generate a silyl nucleophile in an aprotic polar solvent and its 1,4-addition to a,(3-unsaturated enones smoothly proceed' with a catalytic amount of a Cu(I) salt. 1,1,2,2-Tetramethyl-l,2-diphenyldisilane reacts with (CuOTf)_2◇C_6H_6 to give 1,1,2,2-tetramethyl-1,2-diphenyldisiloxane at room temperature in DMI. In the presence of a,b-enones, the conjugate silylation smoothly proceeds to give the corresponding 3-silylated product in good yields (up to 100%) even with 5 mol% (10 mol% for Cu(I)) of (CuOTf)_2◇C_6H_6 and tributylphosphine (11 mol%) in DMF, DMI and diglyme. This reaction is successfully applied to hexamethyldisilane to generate a trimethylsilyl nucleophile, hitherto not easily accessible. A plausible reaction mechanism via the regeneration of CuOTf in a catalytic cycle is proposed5.Boration of an α,β-enone using a diboron promoted by a copper(I)-phosphine mixture catalystThe Cu(I)-catalyzed boration of an a,(3-enone using a diboron is described. Combination of a Cu(I) salt and tributylphosphine is an effective catalyst system, though the individual use of Cu(I) and tributylphosphine is not active far the reaction6.An Unprecedented Catalytic Reaction Using Gold(I) ComplexesThis paper describes that Au complexes efficiently catalyze dehydrogenative dimerization of trialkylstannanes and its catalytic activity is extensively high (0.1 mol%, 48 h) as comparable to the Pd catalysts Less

以下结果通过从铜（I）盐和氢硅烷过量使用的方法中，与芳族酮和烯烃相结合的烯烃和烯烃与芳族的酮和烯烃相结合。 E电子转移过程作为AS-AS AS氢化物的亲核反应，将促进选择性的选择性。符号含量的羰基的化学选择性还原。使用铜（i）盐（i）salttheβ的conteriveientials c悔，β-烯烃的β-烯烃……使用disilanes的α，β-烯酮更加平稳地进行在升高温度下，容易获得的铜（i）盐，cucl量有效，即使在较低的温度下，cu_2o的slythation cu_2o也有效。 llated酮。4。新方法使用由coppper催化的diailane（i）催化的diaslane将diaselane与Cu（i）盐的反应有效诱导Si-Si-Si-Si-si的裂解的新方法键CC产生铜（i）盐的质极太阳能太阳能溶液量。 DMI房间的2-二苯乙烷。 DMF，DMI和DIGLYME中的三丁基膦（11 mol％）成功地应用于六甲基二硅烷，以生成三甲基硅烷基的核核核酸盐配置。 cu（i）盐和三丁基膦的离子是一种效应催化剂系统，尽管单个使用铜（i）和三丁基膦的用法远远不可以反应。试验kylstannes的脱氢二聚化及其催化剂紧张（0.1 mol）％，48 h），与PD催化剂相当较低

项目成果

A.Hosomi: "Optically Active Lithium-Alkoxide Catalyzed Asymmetric Reduction of Imines with Trimethoxyhydrosilane"Synlett. 4. 561-563 (2003)

A.Hosomi：“光学活性锂醇盐催化亚胺与三甲氧基氢硅烷的不对称还原”Synlett。

Makoto Hojo, Kyosuke Sakata, Nobuo Ushioda, Takeshi Watanabe, Hisashi Nishikori, Akira Hosomi: "Reductive Generation of Enolates Using Chromium(III) Ate-Type Reagent as a Reductant and Reactions of the Enolates with Electrophiles"Organometallics. 20(24).

Makoto Hojo、Kyosuke Sakata、Nobuo Ushioda、Takeshi Watanabe、Hisashi Nishikori、Akira Hosomi：“使用铬(III) Ate型试剂作为还原剂还原烯醇化物以及烯醇化物与亲电子试剂的反应”有机金属。

A.Hosomi: "Homoaldol and Aldol Reactions from Common Enolates and Oxiranes : Reaction of Reductively Generated Chromium Enolates through Cationic Rearrangement"Chem.Lett. 2. 142-143 (2002)

A.Hosomi：“常见烯醇化物和环氧乙烷的同醛醇和羟醛反应：通过阳离子重排还原生成铬烯醇化物的反应”Chem.Lett。

A. Hosomi: "Allyl- and Propargylchromium Reagents Generated by a Chromium(III) Ate-type Reagent as a Reductant and their Reactions with Electrophiles"Chem. Commun.. 4. 357-358 (2001)

A. Hosomi：“由铬(III) Ate型试剂作为还原剂生成的烯丙基和炔丙基铬试剂及其与亲电子试剂的反应”Chem。

Katsukiyo Miura, Tatsuyuki Takahashi, Takeshi Hondo, Akira Hosomi: "12-Sityl-Migrative Cyclization of Vinylsilanes Bearing an Amino Group"Chrality. 15(1). 41-52 (2003)

Katsukiyo Miura、Tatsuyuki Takahashi、Takeshi Hondo、Akira Hosomi：“带有氨基的乙烯基硅烷的 12-Sityl 迁移环化”Chrality。