Iridium-Catalyzed Preparation of Silylboranes by Silane Borylation and Their Use in the Catalytic Borylation of Arenes
Iridium-Catalyzed Preparation of Silylboranes by Silane Borylation and Their Use in the Catalytic Borylation of Arenes
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DOI：
10.1021/om800696d
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发表时间：
2008-11-24
期刊：
影响因子：
2.8
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Boebel, Timothy A.;Hartwig, John F.
甲硅烷基硼烷是过渡金属催化的不饱和有机分子反应的通用试剂。这些试剂通常通过将甲硅烷基锂物质添加到硼亲电试剂中来制备。然而，产生阴离子硅烷试剂的需要限制了可容易获得的甲硅烷基硼烷的范围。在这里，我们描述的合成，三烷基甲硅烷基硼烷的硅烷的硼化铱配合物催化。三烷基氢硅烷与B（2）Pin（2）在[Ir（OMe）cod]（2）和4，4 '-二叔丁基联吡啶的组合催化下反应形成三烷基甲硅烷基硼酸酯。此外，我们表明，这些三烷基甲硅烷基硼烷作为铱催化硼化芳基C-H键的硼源。与二硼试剂相反，甲硅烷基硼烷在芳基和甲基C-H键处与甲基芳烃反应。
Silylboranes are versatile reagents for transition metal-catalyzed reactions of unsaturated organic molecules. These reagents are typically prepared by the addition of a silyl lithium species to a boron electrophile. However, the need to generate anionic silane reagents limits the scope of silylboranes that can be readily obtained. Here, we describe the synthesis,of trialkylsilylboranes by the borylation of silanes catalyzed by iridium complexes. The reaction of trialkylhydrosilanes with B(2)Pin(2) catalyzed by the combination of [Ir(OMe)cod](2) and 4,4'-di-tert-butylbipyridine forms trialkylsilylboronic esters. In addition, we show that these trialkylsilylboranes serve as boron sources for the iridium-catalyzed borylation of aryl C-H bonds. In contrast to diboron reagents, the silylboranes react with methylarenes at both the aryl and methyl C-H bonds.