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首页> 外文期刊>Nature >Deacylative transformations of ketones via aromatization-promoted C-C bond activation
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Deacylative transformations of ketones via aromatization-promoted C-C bond activation

机译：酮通过芳构化促进的C-C键活化进行脱酰基转化

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摘要

Carbon-hydrogen (C-H) and carbon-carbon (C-C) bonds are the main constituents of organic matter. Recent advances in C-H functionalization technology have vastly expanded our toolbox for organic synthesis1. By contrast, C-C activation methods that enable editing of the molecular skeleton remain limited(2-7). Several methods have been proposed for catalytic C-C activation, particularly with ketone substrates, that are typically promoted by using either ring-strain release as a thermodynamic driving force(4,6) or directing groups(5,7) to control the reaction outcome. Although effective, these strategies require substrates that contain highly strained ketones or a preinstalled directing group, or are limited to more specialist substrate classes(5). Here we report a general C-C activation mode driven by aromatization of a pre-aromatic intermediate formed in situ. This reaction is suitable for various ketone substrates, is catalysed by an iridium/phosphine combination and is promoted by a hydrazine reagent and 1,3-dienes. Specifically, the acyl group is removed from the ketone and transformed to a pyrazole, and the resulting alkyl fragment undergoes various transformations. These include the deacetylation of methyl ketones, carbenoid-free formal homologation of aliphatic linear ketones and deconstructive pyrazole synthesis from cyclic ketones. Given that ketones are prevalent in feedstock chemicals, natural products and pharmaceuticals, these transformations could offer strategic bond disconnections in the synthesis of complex bioactive molecules.
机译：碳氢键（C-H）和碳碳键（C-C）是有机物质的主要成分。 C-H功能化技术的最新进展极大地扩展了我们用于有机合成的工具箱1。相比之下，启用分子骨架编辑的C-C激活方法仍然有限（2-7）。已经提出了几种催化C-C活化的方法，特别是使用酮类底物时，通常通过使用环应变释放作为热力学驱动力（4,6）或引导基团（5,7）来控制反应结果而得到促进。尽管有效，但这些策略要求底物包含高张力的酮或预先安装的导向基团，或限于更专业的底物类别（5）。在这里，我们报告了由原位形成的芳族中间体中间体的芳构化驱动的一般C-C活化模式。该反应适用于各种酮底物，由铱/膦结合催化，并由肼试剂和1,3-二烯促进。具体地，从酮上除去酰基并转化为吡唑，并且所得的烷基片段经历各种转化。这些包括甲基酮的去乙酰化，脂肪族线性酮的无类胡萝卜素的正式同系物和从环状酮解构的吡唑合成。考虑到酮在原料化学品，天然产品和药品中普遍存在，这些转变可能会在复杂的生物活性分子的合成中提供战略性的键断开连接。

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  • 来源
    《Nature》 |2019年第7748期|373-378|共6页
  • 作者

    Xu Yan; Qi Xiaotian; Zheng Pengfei; Berti Carlo C.; Liu Peng; Dong Guangbin;

  • 作者单位

    Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 USA;

    Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA;

    Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 USA|Army Med Univ, Coll Pharm, Chongqing, Peoples R China;

    Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 USA;

    Univ Pittsburgh, Dept Chem, Pittsburgh, PA 15260 USA;

    Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 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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