Functionalization of α‐C(sp3)−H Bonds in Amides Using Radical Translocating Arylating Groups

• Published in: Angewandte Chemie International Edition Vol. 60; no. 7; pp. 3561 - 3565
• Main Authors: Radhoff, Niklas, Studer, Armido
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 15-02-2021; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Amides; Aromatic compounds; aryl migration; Communication; Communications; Extrusion; hydrogen atom transfer; radical; Sulfur dioxide; visible light catalysis; aryl migration; radical; visible light catalysis; hydrogen atom transfer
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202013275

α‐C−H arylation of N‐alkylamides using 2‐iodoarylsulfonyl radical translocating arylating (RTA) groups is reported. The method allows the construction of α‐quaternary carbon centers in amides. Various mono‐ and disubstituted RTA‐groups are applied to the arylation of primary, secondary, and tertiary α‐C(sp3)−H‐bonds. These radical transformations proceed in good to excellent yields and the cascades comprise a 1,6‐hydrogen atom transfer, followed by a 1,4‐aryl migration with subsequent SO2 extrusion.
α‐C−H arylation of N‐alkylamides using 2‐iodoarylsulfonyl radical translocating arylating (RTA) groups is reported. The RTA group fulfills multiple roles: It acts as radical precursor, engages in remote C−H activation via hydrogen atom transfer, and serves as arylating moiety. The method allows the construction of α‐quaternary carbon centers in amides and shows broad substrate scope.