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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

基本信息

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

项目摘要

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

本研究项目取得了以下成果1.铜(I)盐和氢硅烷生成的还原剂的新反应性：选择性还原与芳香族基团共轭的酮和烯烃利用铜(I)盐和氢硅烷制备的试剂将芳香酮和烯烃选择性转化为相应的醇和烷烃。过量使用氢硅烷对于获得高反应性是最重要的。单电子转移过程以及氢化物的亲核反应将有助于选择性2。第一个金络合物催化的有机化合物选择性氢化硅烷化第一个使用催化量的金络合物对有机化合物（例如醛和醛亚胺）进行氢化硅烷化的例子，实现了羰基化合物的多功能区域和化学选择性还原，是描述了3.使用由铜（I）盐介导的乙硅烷进行α，β-烯酮共轭硅烷化的简便方法使用乙硅烷对α，β-烯酮进行共轭硅烷化，通过简单的操作，可以通过化学计量和催化量的易于获得的铜（I）盐顺利进行。在升高的温度下，化学计量的 CuCl 对于甲硅烷基化是有效的。在三氟甲磺酸甲硅烷基酯存在下，使用催化量的Cu_2O甚至在较低温度下也能提供产物。这些方法为b-甲硅烷基化酮的合成提供了方便的工具。4.铜(I)盐催化的乙硅烷将甲硅烷基引入α,β-烯酮的新方法本文描述了乙硅烷与Cu(I)盐的反应有效诱导Si-Si键的断裂，并在非质子极性溶剂中生成甲硅烷基亲核试剂催化量的Cu(I)盐与a,(3-不饱和烯酮的1,4-加成反应顺利进行。1,1,2,2-四甲基-1,2-二苯基二硅烷在室温下与(CuOTf)_2◇C_6H_6反应生成1,1,2,2-四甲基-1,2-二苯基二硅氧烷 DMI。在a,b-烯酮存在下，即使在DMF、DMI和二甘醇二甲醚中使用5 mol%（对于Cu(I)为10 mol%）的(CuOTf)_2◇C_6H_6和三丁基膦（11 mol%），共轭硅烷化反应也能顺利进行，以良好的收率（高达100%）生成相应的3-硅烷化产物。该反应已成功应用于六甲基乙硅烷生成迄今为止不易获得的三甲基甲硅烷基亲核试剂。提出了一种通过催化循环中 CuOTf 再生的合理反应机制5。使用铜（I）-膦混合物催化剂促进的二硼对 α,β-烯酮进行硼化反应Cu(I) 催化的硼化反应描述了使用二硼的a,(3-烯酮。Cu(I)盐和三丁基膦的组合是一种有效的催化剂体系，尽管单独使用Cu(I)和三丁基膦在反应中并不活跃6。使用金(I)络合物的前所未有的催化反应本文描述了Au络合物有效催化三烷基锡烷的脱氢二聚及其与 Pd 催化剂相比，催化活性非常高（0.1 mol%，48 小时）。