Synthesis of Phenanthrenes through Copper-Catalyzed Cross-Coupling of N-Tosylhydrazones with Terminal Alkynes
Synthesis of Phenanthrenes through Copper-Catalyzed Cross-Coupling of N-Tosylhydrazones with Terminal Alkynes
复制标题
铜催化 N-甲苯磺酰腙与末端炔烃交叉偶联合成菲
DOI：
10.1021/jo501489c
复制
发表时间：
2014-09-19
影响因子：
3.6
通讯作者：
Wang, Jianbo
中科院分区：
文献类型：
--
作者：
Hossain, Mohammad Lokman;Ye, Fei;Wang, Jianbo
探索了一种通过铜催化芳香对甲苯磺酰肼与末端炔的反应合成菲的新方法。该反应通过形成烯丙烯中间体和随后的六皮电子环化-异构化反应进行，以良好的产率提供菲的衍生物。该转化可通过两种方式进行：(1)以[1，1‘-联苯]-2-甲醛和末端炔衍生的N-对甲苯基肼为起始原料；(2)以芳香醛和2-炔基联苯衍生的N-对甲苯肼为起始原料。这种新的菲合成方法使用容易获得的原料和廉价的铜催化剂，并且具有广泛的官能团兼容性。
A novel protocol for the synthesis of phenanthrenes through the copper-catalyzed reaction of aromatic tosylhydrazones with terminal alkynes is explored. The reaction proceeds via the formation of an allene intermediate and subsequent six-pi-electron cyclization-isomerization, affording phenanthrene derivatives in good yields. The transformation can be performed in two ways: (1) with N-tosylhydrazones derived from [1,1'-biphenyl]-2-carbaldehydes and terminal alkynes as the starting materials and (2) with N-tosylhydrazones derived from aromatic aldehydes and 2-alkynyl biphenyls as the starting materials. This new phenanthrene synthesis uses readily available starting materials and a cheap copper catalyst and has a wide range of functional group compatibility.