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Chemoselective C−C σ‐Bond Activation of the Most Stable Ring in Biphenylene **
Author(s) -
Kong Richard Y.,
Crimmin Mark R.
Publication year - 2021
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.202011594
Subject(s) - biphenylene , chemoselectivity , chemistry , ring (chemistry) , ring strain , reactivity (psychology) , cleavage (geology) , stereochemistry , bond cleavage , transition state , crystallography , computational chemistry , materials science , organic chemistry , catalysis , phenylene , medicine , polymer , alternative medicine , pathology , fracture (geology) , composite material
The chemoselective cleavage of a six‐membered aromatic ring in biphenylene is reported using an aluminum(I) complex. This type of selectivity is unprecedented. In every example of transition metal mediated C−C σ‐bond activation reported to date, the reaction occurs at the central four‐membered ring of biphenylene. Insight into the origin of chemoselectivity was obtained through a detailed mechanistic analysis (isolation of an intermediate, DFT studies, activation strain analysis). In conclusion, the divergent reactivity can be attributed to differences in both the symmetry and radial extension of the frontier molecular orbitals of the aluminum(I) fragment compared to that of common transition metal fragments.