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  • Title: Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp³)-H bonds.
    Author: Wu X, Zhao Y, Zhang G, Ge H.
    Journal: Angew Chem Int Ed Engl; 2014 Apr 01; 53(14):3706-10. PubMed ID: 24590659.
    Abstract:
    The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp(3) C-H bond functionalization process. The reaction favors predominantly the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds. Moreover, a preference for activating sp(3) C-H bonds of β-methyl groups, via a five-membered ring intermediate, over the aromatic sp(2) C-H bonds was also observed in the cyclometalation step. Additionally, sp(3) C-H bonds of unactivated secondary sp(3) C-H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms.
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