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

本研究取得了以下成果：1.铜（I）盐和氢硅烷生成的还原剂的新反应性：选择性还原与芳香基团共轭的酮和烯烃通过由铜（I）盐和氢硅烷制备的试剂，芳香酮和烯烃被选择性地转化为相应的醇和烷烃。氢硅烷的过量使用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的选择性硅氢化反应描述了使用催化量的金络合物的有机化合物如醛和醛亚胺的硅氢化反应的第一个实例，其实现了羰基化合物的多功能区域和化学选择性还原3. α，铜（I）盐介导的乙硅烷催化合成β-烯酮 ...更多信息 - 使用乙硅烷的α，β-烯酮的甲硅烷基化通过容易的操作用化学计量和催化量的容易获得的铜（I）盐顺利地进行。在升高的温度下，化学计量量的CuCl对于甲硅烷基化是有效的。在三氟甲磺酸硅酯存在下，使用催化量的Cu_2O，即使在较低的温度下也能得到产物。这些方法为合成b-甲硅烷基化酮提供了方便的工具。4.用铜（I）盐催化的乙硅烷在α，β-烯酮中引入甲硅烷基的新方法本文描述了乙硅烷与铜（I）盐的反应有效地诱导Si-Si键的断裂，在非质子极性溶剂中生成甲硅烷基亲核试剂，（3-不饱和烯酮）与催化量的铜（I）盐一起顺利进行。1，1，2，2-四甲基-1，2-二苯基二硅烷与（CuOTf）_2·C_6H_6在室温下反应生成1，1，2，2-四甲基-1，2-二苯基二硅氧烷。在α，b-烯酮存在下，在DMF、DMF和二甘醇二甲醚中，当（CuOTf）_2·C_6H_6和三丁基膦（11mol%）的摩尔比为5%（Cu（I）为10%）时，共轭硅烷化反应仍能顺利进行，得到相应的3-硅烷化产物，产率高达100%。该反应被成功地应用于六甲基二硅烷，以生成三甲基甲硅烷基亲核试剂，迄今为止还不容易获得。5.铜（I）-膦混合催化剂促进的二硼化α，β-烯酮的硼化反应研究了Cu（I）催化的二硼化α，β-烯酮的硼化反应。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）和三丁基膦对反应没有活性。6.一种前所未有的金（I）配合物催化反应本文描述了Au配合物有效地催化三烷基锡烷的二聚反应，其催化活性非常高（0.1 mol%，48 h）与Pd催化剂相当

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