Rhodium(III)-Catalyzed Cascade [5+1] Annulation/5-exo-Cyclization Initiated by C-H Activation: 1,6-Diynes as One-Carbon Reaction Partners
Rhodium(III)-Catalyzed Cascade [5+1] Annulation/5-exo-Cyclization Initiated by C-H Activation: 1,6-Diynes as One-Carbon Reaction Partners
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铑 (III) 催化级联 [5 1] 由 C-H 激活引发的环化/5-外环化：1,6-二炔作为一碳反应伙伴
DOI：
10.1021/acs.orglett.8b01105
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发表时间：
2018
期刊：
影响因子：
5.2
通讯作者：
Du Miao
中科院分区：
文献类型：
--
作者：
Xu Fen;Kang Wei Fen;Wang Yang;Liu Chun Sen;Tian Jia Yue;Zhao Rui Rui;Du Miao
本文报道了脒与二炔的催化[5 + 1]成环/5-外环化反应。该方案提供了高度原子经济的途径，在一个步骤中以高效率和高选择性制备两个含氮杂环。值得注意的是，该反应代表了在C-H官能化中使用二炔作为一碳反应伴侣的第一个实例。动力学同位素效应表明，该反应的催化循环是由脒基N-苯环上的邻位C-H键断裂引发的，这可能参与了限速步骤。基于密度泛函理论（DFT）的计算表明，C-H活化和Rh（V）物种通过5-外环化的形成可能是该级联转化的重要过程。
The catalytic [5 + 1] annulation/5-exo-cyclization reaction of amidines with diynes is reported herein. This protocol provides highly atom-economical access to fabricate two nitrogen-containing heterocycles in one step with high efficiency and selectivity. Significantly, this reaction represents the first example of using diyne as a one-carbon reaction partner in C–H functionalization. Kinetic isotope effects suggested that the catalytic cycle of this reaction is initiated by the cleavage of theorthoC–H bond in theN-phenyl ring of amidines, which is likely involved in the rate-limiting step. Calculations based on density functional theory (DFT) indicated that C–H activation and the formation of Rh(V) species via 5-exo-cyclization could be vital processes for this cascade transformation.