The Fascinating Chemistry of α‐Haloamides. Issue 2 (13th January 2020)

• Record Type: Journal Article
• Authors: Fantinati, Anna; Zanirato, Vinicio; Marchetti, Paolo; Trapella, Claudio
• Is Part Of: ChemistryOpen. Volume 9:Issue 2(2020)
• Page Start: 100
• Page End: 170
• Publication Date: 2020-01-13
• Subjects: amides -- electrochemistry -- photocatalysis -- radical reactions -- reaction mechanisms; Chemistry -- Periodicals; 540; 540.5
• DOI: 10.1002/open.201900220
• Languages: English
• ISSNs: 2191-1363

Abstract

Abstract: The aim of this review is to highlight the rich chemistry of α‐haloamides originally mainly used to discover new C−N, C−O and C−S bond forming reactions, and later widely employed in C−C cross‐coupling reactions with C(sp 3 ), C(sp 2 ) and C(sp) coupling partners. Radical‐mediated transformations of α‐haloamides bearing a suitable located unsaturated bond has proven to be a straightforward alternative to access diverse cyclic compounds by means of either radical initiators, transition metal redox catalysis or visible light photoredox catalysis. On the other hand, cycloadditions with α‐halohydroxamate‐based azaoxyallyl cations have garnered significant attention. Moreover, in view of the important role in life and materials science of difluoroalkylated compounds, a wide range of catalysts has been developed for the efficient incorporation of difluoroacetamido moieties into activated as well as unactivated substrates. Abstract : What can α‐haloamides do ? The α‐haloamide functional group is an efficient platform for a lot of transformations. Its framework, surprisingly rich of chemically "touchable" atoms, has been used for α‐aminations, radical cyclizations to β‐ and γ‐lactams, intra‐ and intermolecular transition metal catalyzed α‐alkylations, α‐alkenylations, α‐alkynylations, α‐arylations, as well as a three‐atom unit for heterocyclic formation.