Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals. Issue 39 (29th August 2018)

• Record Type: Journal Article
• Authors: Morcillo, Sara P.; Dauncey, Elizabeth M.; Kim, Ji Hye; Douglas, James J.; Sheikh, Nadeem S.; Leonori, Daniele
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 39(2018)
• Page Start: 12945
• Page End: 12949
• Publication Date: 2018-08-29
• Subjects: amines -- halogenation -- photochemistry -- radicals -- reaction mechanisms; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201807941
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The selective functionalization of C(sp 3 )−H bonds at distal positions to functional groups is a challenging task in synthetic chemistry. Reported here is a photoinduced radical cascade strategy for the divergent functionalization of amides and protected amines. The process is based on the oxidative generation of electrophilic amidyl radicals and their subsequent transposition by 1, 5‐H‐atom transfer, resulting in remote fluorination, chlorination and, for the first time, thioetherification, cyanation, and alkynylation. The process is tolerant of most common functional groups and delivers useful building blocks that can be further elaborated. The utility of this strategy is demonstrated through the late‐stage functionalization of amino acids and a dipeptide. Abstract : With HAT in hand : Reported here is a photoinduced radical cascade strategy for the divergent functionalization of amides and protected amines. It is based on the oxidative generation of electrophilic amidyl radicals and their subsequent transposition by 1, 5‐H‐atom transfer, which results in remote fluorination, chlorination, thioetherification, cyanation, and alkynylation. This strategy was used for the late‐stage functionalization of amino acids and a dipeptide.