CuOTf-Catalyzed Selective Generation of 2-Aminopyrimidines from Carbodiimides and Diaryliodonium Salts by a Triple C(sp<sup>3</sup>)−H Functionalization
作者:Yue Chi、Haihan Yan、Wen-Xiong Zhang、Zhenfeng Xi
DOI:10.1002/chem.201604739
日期:2017.1.18
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
选择性的C(sp 3)-H键官能化是有机合成中一种理想且原子经济的方法。在这项工作中,通过在碳二亚胺中切割四个C(sp 3)-H,一个C-N和一个C = N键,在碳催化的碳二亚胺和二芳基碘鎓盐之间的反应中生成了2-氨基嘧啶。它是与C = N键相邻的第一个三元C(sp 3)-H键官能化。2-氨基嘧啶的选择性合成受二芳基碘鎓盐的量控制。通过检测重要的中间体和进行DFT计算,可以很好地阐明涉及CN形成/ 1,5-H移位/ 1,7-H移位/ 6π-电环闭环/芳构化的新机制。