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

1.由铜(I)盐和氢硅烷生成的还原试剂的新反应性：由铜(I)盐和氢硅烷制备的试剂选择性地将酮和芳香族基团结合的烯烃和酮转化为相应的醇和烷烃。过量使用氢化硅烷是获得高活性的最重要的因素。第一个金络合物催化的有机化合物的选择性硅氢化第一个例子描述了利用一定量的金络合物催化有机化合物，如醛和乙二胺的硅氢化反应，从而实现了对羰基化合物的多种区域和化学选择性还原。3.铜(I)盐催化的α，β-烯类化合物共轭硅烷化的简便方法使用二硅烷的α，β-烯酮的更多硅烷化反应通过简单的操作，顺利地进行了化学计量比和催化量的容易获得的铜(I)盐。在高温下，化学计量的CuCL对硅烷化反应是有效的。在三氟化硅存在的情况下，即使在较低的温度下，使用催化量的Cu2O也可以得到产物。用铜(I)盐催化二硅烷将硅基引入α，β-烯酮的新方法本文描述了二硅烷与铜(I)盐的反应有效地诱导了硅-硅键的断裂，在非质子性极性溶剂中生成了一个硅基亲核试剂，它与α，(3-不饱和烯酮)的1，4-加成反应在催化量的铜(I)盐的作用下顺利进行。1，1，2，2-四甲基-L，2-二苯基二硅烷与(CuOTf)_2-◇C_6H_6于室温下反应生成1，1，2，2-四甲基-1，2-二苯基二硅氧烷。在a，b-烯酮存在下，即使在二甲基甲酰胺、二甲基咪唑和二甘醇中加入5%的(CuOTf)_2◇C_6H_6和11%的三丁基膦(11%)，共轭硅烷化反应也能以较高的产率(高达100%)得到相应的3-硅烷化产物。该反应被成功地应用于六甲基二硅烷，生成了迄今为止不易获得的三甲基硅基亲核试剂。提出了一种可能的反应机理，即在催化循环中CuOTf的再生。5.铜(I)-膦混合物催化的二硼对α，β-烯酮的硼化反应。铜(I)盐和三丁基膦的组合是一种有效的催化体系，尽管单独使用铜(I)和三丁基膦在反应中活性不高6.用金(I)络合物催化反应是一种史无前例的催化反应.本文描述了Au络合物有效地催化三烷基锡烷的脱氢二聚反应，其催化活性非常高(0.1mol%，48h)，与钯催化剂较少相比

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