CuOTf-Catalyzed Selective Generation of 2-Aminopyrimidines from Carbodiimides and Diaryliodonium Salts by a Triple C(sp3)−H Functionalization
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- 作者：Dr. Yue Chi ; Haihan Yan ; Prof. Dr. Wen-Xiong Zhang and Prof. Dr. Zhenfeng Xi
- 刊名：Chemistry - A European Journal
- 出版年：2017
- 出版时间：January 18, 2017
- 年：2017
- 卷：23
- 期：4
- 页码：757-761
- 全文大小：2239K
- ISSN：1521-3765
文摘
The selective C(sp3)−H bond functionalization is an ideal and atom-economical method in organic synthesis. In this work, 2-aminopyrimidines are generated from a Cu-catalyzed reaction between carbodiimides and diaryliodonium salts, by cleavage of four C(sp3)−H, one C−N, and one C=N bonds in the carbodiimides. It is the first triple C(sp3)−H bond functionalization neighboring a C=N bond. The selective synthesis of 2-aminopyrimidines is controlled by the amount of the diaryliodonium salts. The novel mechanism involving a C−N formation/1,5-H shift/1,7-H shift/6 π-electrocyclic ring-closing/aromatization is well elucidated by the detection of important intermediates and DFT calculations.