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Lanthanide‐Catalyzed Reversible Alkynyl Exchange by Carbon–Carbon Single‐Bond Cleavage Assisted by a Secondary Amino Group
Author(s) -
Shao Yinlin,
Zhang Fangjun,
Zhang Jie,
Zhou Xigeng
Publication year - 2016
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.201605822
Subject(s) - cleavage (geology) , catalysis , chemistry , carbon fibers , lanthanide , bond cleavage , reinforced carbon–carbon , group (periodic table) , combinatorial chemistry , organic chemistry , materials science , composite number , ion , fracture (geology) , composite material
Lanthanide‐catalyzed alkynyl exchange through C−C single‐bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β‐alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo‐ and cross‐dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions.