Hydrogen atom transfer from tertiary alkanamides to the cumyloxyl radical. The role of substrate structure on alkali and alkaline earth metal ion induced C–H bond deactivation. Issue 48 (1st December 2016)

• Record Type: Journal Article
• Authors: Salamone, Michela; Mangiacapra, Livia; Carboni, Giulia; Bietti, Massimo
• Is Part Of: Tetrahedron. Volume 72:Issue 48(2016)
• Page Start: 7757
• Page End: 7763
• Publication Date: 2016-12-01
• Subjects: Alkoxyl radical -- Hydrogen atom transfer -- C–H deactivation -- Laser flash photolysis; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tet.2016.05.047
• Languages: English
• ISSNs: 0040-4020

Abstract

Abstract: The effect of metal ions on the reactions of the cumyloxyl radical with tertiary amides has been studied. With N, N -dialkylacetamides addition of Li + and Ca 2+ leads to strong C–H deactivation, whereas with N, N -dimethylalkanamides deactivation was observed to decrease with increasing the alkanoyl group sterics. C–H deactivation has been rationalized in terms of the increase in the extent of positive charge on the amide determined by metal ion binding. The implications of these findings are discussed in the framework of the development of selective C–H functionalization procedures. Graphical abstract: