title: CuOTf-Catalyzed Selective Generation of 2-Aminopyrimidines from Carbodiimides and Diaryliodonium Salts by a Triple C(sp3)-H Functionalization.
abstract: 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.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Chi
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.
authors.forename: Haihan
authors.initials: H
authors.lastname: Yan
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.|State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China.
authors.forename: Wen-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, P. R. China.
authors.forename: Zhenfeng
authors.initials: Z
authors.lastname: Xi
keywords: 2-aminopyrimidines; C(sp3)−H functionalization; carbodiimide; diaryliodonium salts; hydrogen shift