Premium
Ruthenium‐Catalyzed C−C Bond Cleavage of 2 H ‐Azirines: A Formal [3+2+2] Cycloaddition to Fused Azepine Skeletons
Author(s) -
Li Tengfei,
Xu Fen,
Li Xincheng,
Wang Chunxiang,
Wan Boshun
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.201510820
Subject(s) - azepine , synthon , cycloaddition , ruthenium , chemistry , catalysis , cleavage (geology) , bond cleavage , stereochemistry , materials science , organic chemistry , fracture (geology) , composite material
2 H ‐azirines can serve as three‐atom synthons by C−C bond cleavage, however, it involves a high energy barrier under thermal conditions (>50.0 kcal mol −1 ). Reported is a ruthenium‐catalyzed [3+2+2] cycloaddition reaction of 2 H ‐azirines with diynes, thus leading to the formation of fused azepine skeletons. This approach features an unprecedented metal‐catalyzed C−C bond cleavage of 2 H ‐azirines at room temperature, and the challenging construction of aza‐seven‐membered rings from diynes. The results of this study provide a new reaction pattern for constructing nitrogen‐containing seven‐membered rings and may find applications in the synthesis of other complex heterocycles.