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Cleaving carbon-carbon bonds by inserting tungsten into unstrained aromatic rings

机译：通过将钨插入未应变的芳环中来裂解碳-碳键

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摘要

The cleavage of C-H and C-C bonds by transition metal centres is of fundamental interest and plays an important role in the synthesis of complex organic molecules from petroleum feedstocks. But while there are many examples for the oxidative addition of C-H bonds to a metal centre, transformations that feature oxidative addition of C-C bonds are rare. The paucity of transformations that involve the cleavage of C-C rather than C-H bonds is usually attributed to kinetic factors arising from the greater steric hindrance and the directional nature of the sp~n hybrids that form the C-C bond, and to thermodynamic factors arising from the fact that M-C bonds are weaker than M-H bonds. Not surprisingly, therefore, most examples of C-C bond cleavage either avoid the kinetic limitations by using metal compounds in which the C-C bond is held in close proximity to the metal centre, or avoid the thermodynamic limitations by using organic substrates in which the cleavage is accompanied by either a relief of strain energy or the formation of an aromatic system. Here, we show that a tungsten centre can be used to cleave a strong C-C bond that is a component of an unstrained 6-membered aromatic ring. The cleavage is enabled by the formation of an unusual chelating di(isocyanide) ligand, which suggests that other metal centres with suitable ancillary ligands could also accomplish the cleavage of strong C-C bonds of aromatic substrates and thereby provide new ways of functionalizing such molecules.
机译：过渡金属中心对C-H和C-C键的裂解具有根本的意义，并且在由石油原料合成复杂的有机分子中起着重要的作用。但是，尽管有许多将C-H键氧化加成至金属中心的例子，但很少有以C-C键氧化加成为特征的转变。涉及CC而不是CH键断裂的转化很少，通常归因于更大的位阻和形成CC键的spn杂种的方向性引起的动力学因素，以及归因于该事实的热力学因素MC债券比MH债券弱。因此，毫不奇怪，大多数CC键断裂的例子要么通过使用其中CC键紧密靠近金属中心的金属化合物来避免动力学限制，要么通过使用伴随断裂的有机底物来避免热力学限制。通过释放应变能或形成芳香体系。在这里，我们表明钨中心可用于裂解强C-C键，该C-C键是未应变的6元芳环的组成部分。裂解是通过形成异常的螯合二（异氰化物）配体实现的，这表明具有合适辅助配体的其他金属中心也可以完成芳族底物强C-C键的裂解，从而提供了功能化此类分子的新方法。

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  • 来源
    《Nature》 |2010年第7280期|523-526|共4页
  • 作者

    Aaron Sattler; Gerard Parkin;

  • 作者单位

    Department of Chemistry, Columbia University, New York, New York 10027, USA;

    Department of Chemistry, Columbia University, New York, New York 10027, 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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  • 正文语种 eng
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