2,2'-Biquinoline-Based Recyclable Electroauxiliaries for the Generation of Alkyl Radicals via C-C Bond Cleavage.

Abstract

Alkyl radical precursors are essential for a wide variety of photocatalytic and 3d-metal-catalyzed C-C bond forming reactions. Neutral organic heterocycles as electroauxiliaries such as 4-alkyl Hantzsch esters have become reliable tools for alkyl radical formation. Here we show that 2,2'-biquinoline-derived alkyl-substituted dihydroquinolines act as competent radical precursors with the ability to form primary, secondary and tertiary alkyl radicals. Hydroalkylation of benzalmalononitriles and N-Boc protected diazenes has been achieved through copper catalysis under mild conditions of 50 °C with good to very good yields of up to 85 %. Furthermore, the dihydroquinolines' reactivity towards a denitrative alkylation of nitroolefins such as β-nitrostyrene was discovered. Most importantly, the released biquinoline can be recycled, which greatly improves the overall atom-economy of these alkyl radical precursors in comparison to previous N-heterocyclic electroauxiliaries.