Meta-Selective CAr-H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy
Meta-Selective CAr-H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy
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通过 Ru3(CO)12 催化的邻位金属化策略对芳烃进行间位选择性 CAr-H 硝化
DOI：
10.1021/jacs.6b03402
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发表时间：
2016-07-13
影响因子：
15
通讯作者：
Zhang, Ao
中科院分区：
文献类型：
--
作者：
Fan, Zhoulong;Ni, Jiabin;Zhang, Ao
描述了过渡金属催化的芳烃间位选择性 C-Ar-H 硝化的第一个例子。以Ru-3(CO)(12)为催化剂，以Cu(NO3)(2)中心点3H(2)O为硝基源，以间位选择性硝化了多种带有多种N-杂环或肟基作为导向基团的芳烃。机理研究表明，新的 18e-八面体钌物种作为关键的邻-C-Ar-H 金属化中间体的形成，可能是随后的间位选择性亲电芳香取代（SEAr）的原因。此外，这种方法为许多有用的药物分子的原子/步骤经济合成提供了快速通道策略。
The first example of transition metal-catalyzed meta-selective C-Ar-H nitration of arenes is described. With the use of Ru-3(CO)(12) as the catalyst and Cu(NO3)(2)center dot 3H(2)O as the nitro source, a wide spectrum of arenes bearing diversified N-heterocycles or oximido as the directing groups were nitrated with meta selectivity exclusively. Mechanism studies have demonstrated the formation of a new 18e-octahedral ruthenium species as a key ortho-C-Ar-H metalated intermediate, which may be responsible for the subsequent meta-selective electrophilic aromatic substitution (SEAr). Moreover, this approach provides a fast-track strategy for atom/step economical synthesis of many useful pharmaceutical molecules.