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Visible‐Light‐Induced ortho ‐Selective Migration on Pyridyl Ring: Trifluoromethylative Pyridylation of Unactivated Alkenes
Author(s) -
Jeon Jinwon,
He YuTao,
Shin Sanghoon,
Hong Sungwoo
Publication year - 2020
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.201912746
Subject(s) - pyridinium , alkene , chemistry , radical , intramolecular force , nucleophile , alkyl , ring (chemistry) , surface modification , salt (chemistry) , combinatorial chemistry , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis
The photocatalyzed ortho ‐selective migration on a pyridyl ring has been achieved for the site‐selective trifluoromethylative pyridylation of unactivated alkenes. The overall process is initiated by the selective addition of a CF 3 radical to the alkene to provide a nucleophilic alkyl radical intermediate, which enables an intramolecular endo addition exclusively to the ortho ‐position of the pyridinium salt. Both secondary and tertiary alkyl radicals are well‐suited for addition to the C2‐position of pyridinium salts to ultimately provide synthetically valuable C2‐fluoroalkyl functionalized pyridines. Moreover, the method was successfully applied to the reaction with P‐centered radicals. The utility of this transformation was further demonstrated by the late‐stage functionalization of complex bioactive molecules.