Fluorine Effects on Group Migration via a Rhodium(V) Nitrenoid Intermediate

An unprecedented rhodium(III)‐catalyzed hydroarylation of α,α‐difluoromethylene alkynes with N‐pivaloxyl aroylamides through sequential C−H activation and aryl migration is detailed herein. A large array of α,α‐difluoromethylene alkynes and N‐pivaloxyl aryl amides were amenable to this transformatio...

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Bibliographic Details
Published in:Angewandte Chemie 2017-11, Vol.129 (47), p.15114-15118
Main Authors: Wang, Cheng‐Qiang, Zhang, Yu, Feng, Chao
Format: Article
Language:English
Subjects:
Alkynes
Amides
Aniline
Aromatic compounds
C-H-Aktivierung
Chemistry
Fluoreffekte
Fluorine
Hydroarylierungen
Lossen-Umlagerung
Migration
Organic compounds
Regioselectivity
Rhodium
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Summary:An unprecedented rhodium(III)‐catalyzed hydroarylation of α,α‐difluoromethylene alkynes with N‐pivaloxyl aroylamides through sequential C−H activation and aryl migration is detailed herein. A large array of α,α‐difluoromethylene alkynes and N‐pivaloxyl aryl amides were amenable to this transformation, thus providing a novel synthetic protocol for the construction of difluorinated 2‐alkenyl aniline derivatives in high yields and with excellent regioselectivity. Notably, unique fluorine effects were found to underlie the thus unconventional reaction manifold. Neue Wege erkunden: Die Rhodium(III)‐katalysierte Hydroarylierung von α,α‐Difluormethylenalkinen mit N‐Pivaloyloxyarylamiden ermöglicht die effiziente regiospezifische Synthese von difluorierten 2‐Alkenylanilinen (siehe Schema). Die Fluorsubstituenten in den Alkinsubstraten lenken den Reaktionsverlauf vom konventionellen Anellierungsweg hin zu einem Hydroarylierungsprozess, der eine Lossen‐Umlagerung einschließt.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201708505