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Revisiting Arene C(sp 2 )−H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway
Author(s) -
Hwang Yeongyu,
Park Yoonsu,
Kim Yeong Bum,
Kim Dongwook,
Chang Sukbok
Publication year - 2018
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.201808892
Subject(s) - intramolecular force , iridium , chemistry , amination , electrophile , combinatorial chemistry , catalysis , electrophilic substitution , electrophilic aromatic substitution , stereochemistry , medicinal chemistry , organic chemistry
Two mechanistic pathways, that is, electrocyclization and electrophilic aromatic substitution, are operative in most intramolecular C−H amination reactions proceeding by metal nitrenoid catalysis. Reported here is an alternative mechanistic scaffold leading to benzofused δ‐lactams selectively. Integrated experimental and computational analysis revealed that the reaction proceeds by a key spirocyclization step followed by a skeletal rearrangement. Based on this mechanistic insight, a new synthetic route to spirolactams has been developed.