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Cycloamidination of Aminoalkenes with Nitriles: Synthesis of Substituted 2‐Imidazolines and Tetrahydropyrimidines
Author(s) -
Huang Shujian,
Shao Yinlin,
Zhang Lixin,
Zhou Xigeng
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201508442
Subject(s) - hydroamination , lanthanide , intramolecular force , nitrile , chemistry , combinatorial chemistry , reaction conditions , catalysis , rare earth , computational chemistry , organic chemistry , mineralogy , ion
The first catalytic cycloamidination of aminoalkenes with nitriles has been achieved by using rare‐earth complexes. This reaction is equivalent to the desired intramolecular hydroamination of alkenylamidines, and allows a new direct access to substituted 2‐imidazolines and tetrahydropyrimidines in high yields under operationally simple reaction conditions. Moreover, the methodology is also efficient for synthesis of symmetric and unsymmetric bridged diimidazolines. Compared with the traditional stepwise‐mediated synthetic approaches, the present method avoids the use of additives and harsh reaction conditions, and thus leads to a completely different product distribution. Mechanistic data suggest that the reaction involves the initial NH activation by lanthanide complex followed by nitrile insertion into a LnN bond to form an amidinate lanthanide intermediate which undergoes the cyclization.