Cu- or Fe-catalyzed C–H/C–C bond nitrogenation reactions for the direct synthesis of N-containing compounds
Cu- or Fe-catalyzed C–H/C–C bond nitrogenation reactions for the direct synthesis of N-containing compounds
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DOI：
10.1039/c4qo00350k
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发表时间：
2015-03
影响因子：
5.4
通讯作者：
Yu-Feng Liang;Yu-Feng Liang;N. Jiao
中科院分区：
文献类型：
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作者：
Yu-Feng Liang;Yu-Feng Liang;N. Jiao
含氮化合物广泛存在于天然产物和合成化合物中，例如，它们出现在功能材料、畅销药物以及生物活性分子中。因此，有机化学家在开发新的制备方法方面给予了相当大的关注。为了以绿色和可持续的方式合成这些化合物，研究人员一直致力于通过C-H和/或C-C键裂解将碳氢化合物直接功能化。尽管在简单碳氢化合物的直接功能化方面取得了重大进展，但由于化学键的惰性和某些n源在氧化条件下的不稳定性，通过C-H和/或C-C键裂解将n原子直接结合到简单底物中仍然具有挑战性。叠氮化物试剂常被用作氮源，用于将氮转化为碳骨架。虽然确切的反应途径尚不清楚，但详细的机理研究表明，含有叠氮基团的碳阳离子可能作为关键中间体存在，并通过施密特式重排生成腈、四氮唑、芳胺或其他含氮化合物。考虑到重金属的高成本和毒性，铜和铁作为廉价、易得的金属已经显示出其独特的用途。本帐户试图集中在通过Cu和Fe催化的C-H / C-C键氮化反应，以及它们在合成化学中的应用。
Nitrogen-containing compounds are widely present in both natural products and synthetic compounds, for example, they show up within functional materials, top-selling drugs, as well as bioactive molecules. Thus, organic chemists have paid considerable attention in developing novel methodologies for their preparation. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C–H and/or C–C bond cleavage. Although significant progress has been made in the direct functionalization of simple hydrocarbons, direct incorporation of N-atoms into simple substrates via C–H and/or C–C bond cleavage remains challenging due to the inert chemical bonds and the unstable character of some N-sources under oxidative conditions. Azide reagents are frequently used as nitrogen source in incorporating nitrogen into carbon skeletons. Although the exact reaction pathway remains unclear, detailed mechanistic studies revealed that the carbon cation containing the azido group may exist as the key intermediate which would undergo Schmidt-type rearrangement to afford nitriles, tetrazoles, arylamines, or other kinds of nitrogen-containing compounds. Considering the high cost and toxicity of heavy metals, copper and iron, as inexpensive, readily accessible metals have already shown their unique utilities. This account attempts to focus on C–H/C–C bond nitrogenation reactions via Cu and Fe catalysis, as well as their applications in synthetic chemistry.