Transition-Metal-Free O-, S-, and N-Arylation of Alcohols, Thiols, Amides, Amines, and Related Heterocycles
Transition-Metal-Free O-, S-, and N-Arylation of Alcohols, Thiols, Amides, Amines, and Related Heterocycles
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DOI：
10.1021/jo1022052
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发表时间：
2011-01-21
影响因子：
3.6
通讯作者：
Yus, Miguel
中科院分区：
文献类型：
--
作者：
Cano, Rafael;Ramon, Diego J.;Yus, Miguel
描述了一种在没有任何过渡金属催化剂的情况下对不同芳族杂环进行乌尔曼型芳基化过程的新方案，这意味着使用过量的氢氧化钾和二甲亚砜的组合。该反应可以在多种起始亲核试剂之间进行，包括苯酚、醇、胺、含氮五元体系（如吡唑、咪唑和吲哚）以及具有卤代芳烃、碘化物和溴化物衍生物的酰胺，从而获得最佳结果，可能的途径涉及原位生成相应的苯炔中间体。当2-碘苯胺与甲酰胺或异硫氰酸酯衍生物反应时，得到相应的苯并唑衍生物。
A new protocol for the Ullmann-type arylation process of different aromatic heterocycles without any transition-metal catalyst, implying the use of a combination of an excess of potassium hydroxide and dimethyl sulfoxide, is described. The reaction can be performed between a broad range of starting nucleophiles including phenol, alcohols, amines, nitrogen-containing five-membered systems such as pyrazoles, imidazoles, and indoles, and amides with haloarenes, iodide and bromide derivatives giving the best results, the possible pathway involving the in situ generation of the corresponding benzyne intermediate. When the reaction was performed with 2-iodoaniline and either carboxarnides or isothiocyanato derivatives, the corresponding benzoazole derivatives were obtained.