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Silylation of C-H bonds in aromatic heterocycles by an Earth-abundant metal catalyst

机译：富含地球的金属催化剂将芳族杂环中的C-H键甲硅烷基化

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摘要

Heteroaromatic compounds containing carbon-silicon (C-Si) bonds are of great interest in the fields of organic electronics and photonics, drug discovery, nuclear medicine and complex molecule synthesis, because these compounds have very useful physicochemical properties. Many of the methods now used to construct heteroaromatic C-Si bonds involve stoichiometric reactions between heteroaryl or-ganometallic species and silicon electrophiles or direct, transition-metal-catalysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the presence of excess hydrogen acceptors. Both approaches are useful, but their limitations include functional group incompatibility, narrow scope of application, high cost and low availability of the catalysts, and unproven scalability. For this reason, a new and general catalytic approach to heteroaromatic C-Si bond construction that avoids such limitations is highly desirable. Here we report an example of cross-dehydrogenative heteroaromatic C-H functionalization catalysed by an Earth-abundant alkali metal species. We found that readily available and inexpensive potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, furnishing heteroarylsilanes in a single step. The silylation proceeds under mild conditions, in the absence of hydrogen acceptors, ligands or additives, and is scalable to greater than 100 grams under optionally solvent-free conditions. Substrate classes that are difficult to activate with precious metal catalysts are silylated in good yield and with excellent regioselectivity. The derived heteroarylsilane products readily engage in versatile transformations enabling new synthetic strategies for heteroaromatic elaboration, and are useful in their own right in pharmaceutical and materials science applications.
机译：含有碳-硅（C-Si）键的杂芳族化合物在有机电子学和光子学，药物发现，核医学和复杂分子合成领域中非常受关注，因为这些化合物具有非常有用的理化性质。现在，用于构建杂芳族C-Si键的许多方法涉及杂芳基或-氨基金属物种与硅亲电子试剂之间的化学计量反应，或在铑或铱配合物存在下使用铑或铱配合物直接，过渡金属催化的分子间碳氢（CH）甲硅烷基化。多余的氢受体。两种方法都是有用的，但是它们的局限性包括官能团不相容，应用范围狭窄，催化剂的高成本和低可用性以及未经证实的可扩展性。由于这个原因，非常需要避免这种局限性的杂芳C-Si键结构的新的通用催化方法。在这里，我们报告了一个由地球上丰富的碱金属物种催化的跨脱氢杂芳烃C-H功能化的例子。我们发现，容易获得且便宜的叔丁醇钾催化芳香杂环与氢硅烷的直接甲硅烷基化，一步就可以提供杂芳基硅烷。甲硅烷基化反应在温和条件下进行，没有氢受体，配体或添加剂，并且在可选的无溶剂条件下可扩展至大于100克。难以用贵金属催化剂活化的底物种类以高收率和优异的区域选择性被甲硅烷基化。衍生的杂芳基硅烷产品可以轻松地进行多种转化，从而实现杂芳烃精制的新合成策略，并且在制药和材料科学应用中也很有用。

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  • 来源
    《Nature》 |2015年第7537期|80-84|共5页
  • 作者

    Anton A. Toutov; Wen-Bo Liu; Kerry N. Betz; Alexey Fedorov; Brian M. Stoltz; Robert H. Grubbs;

  • 作者单位

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA;

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA;

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA;

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA,Department of Chemistry and Applied Biosciences, ETH Zuerich, Vladimir Prelog Weg 2, CH-8093 Zuerich. Switzerland;

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA;

    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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