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首页> 外文期刊>Chemistry: A European journal >Cobalt-Mediated Radical Coupling (CMRC): An Unusual Route to Midchain-Functionalized Symmetrical Macromolecules
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Cobalt-Mediated Radical Coupling (CMRC): An Unusual Route to Midchain-Functionalized Symmetrical Macromolecules

机译：钴介导的自由基偶联（CMRC）：通往中链功能化对称高分子的不寻常途径

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摘要

Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by cobalt-mediated radical polymerization (CMRP). Mechanistic features that make this process so efficient for radical polymer coupling are reported here. The mechanism was established on the basis of NMR spectroscopy and MALDI-MS analyses of the coupling product and corroborated by DFT calculations. A key feature of CMRC is the preferential insertion of two diene units in the middle of the chain of the coupling product mainly according to it trans-1,4-addition pathway. The large tolerance of CMRC towards the diene Structure is demonstrated and the impact of this new Coupling method on macromolecular engineering is discussed, especially for midchain functionalization of polymers. It is worth noting that the interest in CMRC goes beyond the field of polymer chemistry. since it constitutes a novel carbon-carbon bond formation method that could be applied to small organic molecules.
机译：钴介导的自由基偶联（CMRC）是合成对称大分子的直接方法，它依赖于将1，3-二烯化合物加到通过钴介导的自由基聚合（CMRP）形成的聚合物前体上。在此报道了使该方法对自由基聚合物偶联如此有效的机理特征。该机理是基于NMR光谱和偶联产物的MALDI-MS分析建立的，并通过DFT计算得到了证实。 CMRC的关键特征是主要根据其反式1,4-加成途径优先在偶联产物链的中间插入两个二烯单元。证明了CMRC对二烯结构的大耐受性，并讨论了这种新的偶联方法对高分子工程的影响，特别是对于聚合物的中链功能化。值得注意的是，对CMRC的兴趣已超出了聚合物化学领域。因为它构成了一种新颖的碳-碳键形成方法，可以应用于有机小分子。

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