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Development, Scope and Mechanisms of Multicomponent Reactions of Asymmetric Electron‐Deficient Alkynes with Amines and Formaldehyde
Author(s) -
Cao Hua,
Wang Xiujun,
Jiang Huanfeng,
Zhu Qiuhua,
Zhang Min,
Liu Haiyang
Publication year - 2008
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.200801471
Subject(s) - regioselectivity , hydroamination , catalysis , formaldehyde , chemistry , pyrimidine , density functional theory , combinatorial chemistry , organic chemistry , computational chemistry , stereochemistry
Based on the reactive behaviour of the substrates, two synthetic routes to polysubstituted pyrimidine derivatives are presented herein: 1) A catalyst‐free multicomponent reaction of electron‐deficient alkynes, aliphatic amines and formaldehyde and 2) Ag I ‐catalyzed synthesis of pyrimidines from electron‐deficient alkynes, anilines and formaldehyde by a domino reaction. Under optimized conditions, the multicomponent reactions were accomplished with high regioselectivity and excellent yields. A computational study was carried out by using the B3LYP density functional theory to elucidate the mechanisms of the catalyst‐free hydroamination reaction. Calculations showed the activation free energies of aliphatic amines were lower than those of anilines, which is consistent with the experimental results.