An Adventure in Sustainable Cross-Coupling of Phenols and Derivatives via Carbon–Oxygen Bond Cleavage
An Adventure in Sustainable Cross-Coupling of Phenols and Derivatives via Carbon–Oxygen Bond Cleavage
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DOI：
10.1021/acscatal.6b02964
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发表时间：
2017-01
期刊：
影响因子：
12.9
通讯作者：
Huiying Zeng;Zihang Qiu;Alejandra Dominguez-Huerta;Zoë Hearne;Zhengwang Chen;Chao‐Jun Li
中科院分区：
文献类型：
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作者：
Huiying Zeng;Zihang Qiu;Alejandra Dominguez-Huerta;Zoë Hearne;Zhengwang Chen;Chao‐Jun Li
芳基卤化物是非常有用的亲电子试剂，可用于通过金属催化的交叉偶联反应合成各种取代的芳香族化合物。由于其合成成本较高，并且使用芳基卤化物原料时会产生化学计量的卤化物废物，因此人们正在探索更便宜且更可持续的替代品，例如苯酚。然而，酚类具有非常活泼的羟基和具有高解离能的C-O键。为了克服这些挑战，早期的研究重点是寻找方法来降低C-O键的能量，同时通过将苯酚转化为苯酚衍生物（例如磺酸盐、酯、氨基甲酸酯、醚和金属盐）来去除活性质子。更大的目标是通过 C-O 裂解将苯酚与亲核试剂直接交叉偶联。在这篇文章中，我们简要总结了有关苯酚衍生物和苯酚交叉偶联的努力和成就。
Aryl halides are very useful electrophiles for synthesizing various substituted aromatic compounds via metal-catalyzed cross-coupling reactions. Because of the high cost associated with their synthesis and the stoichiometric halide waste produced when using aryl halide feedstocks, cheaper and more sustainable alternatives have been explored, such as phenols. However, phenols have a very reactive hydroxyl group and a C–O bond with high dissociation energy. To overcome such challenges, earlier studies focused on finding ways to reduce the energy of the C–O bond while removing the active proton by transforming phenols into phenol derivatives (e.g., sulfonates, esters, carbamates, ethers, and metal salts). A greater ambition is to directly cross-couple phenols with nucleophiles via C–O cleavage. In this Perspective, we briefly summarize efforts and accomplishments concerning the cross-coupling of phenol derivatives and phenols.