Revisiting Arene C(sp2)−H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway

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. Integ...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (41), p.13565-13569
Main Authors: Hwang, Yeongyu, Park, Yoonsu, Kim, Yeong Bum, Kim, Dongwook, Chang, Sukbok
Format: Article
Language:English
Subjects:
Amination
Catalysis
Computer applications
C−H amidation
Iridium
Organic compounds
reaction mechanisms
rearrangements
spirocompounds
Substitution reactions
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Skeleton crew: A spirocyclization and subsequent skeletal rearrangement were identified in the reaction pathway for the iridium‐catalyzed arene C(sp2)−H amidation of phenylalkyl dioxazolones. This mechanistic insight led to the development of an efficient and selective synthetic route to spirolactams and benzolactams.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201808892