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CuOTf‐Catalyzed Selective Generation of 2‐Aminopyrimidines from Carbodiimides and Diaryliodonium Salts by a Triple C(sp 3 )−H Functionalization
Author(s) -
Chi Yue,
Yan Haihan,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604739
Subject(s) - surface modification , catalysis , chemistry , triple bond , combinatorial chemistry , medicinal chemistry , organic chemistry , double bond
The selective C(sp 3 )−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(sp 3 )−H, one C−N, and one C=N bonds in the carbodiimides. It is the first triple C(sp 3 )−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.