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Decyanative Cross‐Coupling of Cyanopyrimidines with O‐, S‐, and N‐Nucleophiles: A Route to Alkoxylpyrimidines, Aminopyrimidines and Alkylthiopyrimidines
Author(s) -
Wei Xiangyang,
Zhang Caiyang,
Wang Yifei,
Zhan Qi,
Qiu Guiying,
Fan Ling,
Yin Guodong
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201901364
Subject(s) - chemistry , intramolecular force , nucleophile , halide , substrate (aquarium) , hydrogen bond , nitrogen atom , medicinal chemistry , coupling reaction , coupling (piping) , stereochemistry , photochemistry , organic chemistry , molecule , catalysis , group (periodic table) , mechanical engineering , engineering , oceanography , geology
The transition metal‐free cross‐coupling reactions of cyanopyrimidines with aliphatic alcohols, thiols (or S ‐alkylisothiourea salts) and amines, giving the corresponding alkoxylpyrimidines, aminopyrimidines, and alkylthiopyrimidines, are reported. Preliminary mechanistic studies reveal that it probably involves a sequential nucleophilic addition‐intramolecular rearrangement process, which is promoted by an intramolecular N–H ··· N five‐membered hydrogen bonding interaction. The presence of a nitrogen atom next to the cyano group is indispensable. The wide substrate scope with excellent yields makes cyanopyrimidines a promising alternative substrate class to the frequently used pyrimidines halides for the formation of C–O, C–S, and C–N bonds through the decyanative cross‐coupling reaction.