Cp*Co(III)-Catalyzed Selective C8-Olefination and Oxyarylation of Quinoline N -Oxides with Terminal Alkynes.

Herein we report Cp*Co(III)-catalyzed site-selective (C8)-H olefination and oxyarylation of quinoline N -oxides with terminal alkynes. The selectivity for C8-olefination and oxyarylation is sterically and electronically controlled. In the case of quinoline N -oxides (unsubstituted at the C2 position), only the olefination product was obtained irrespective of the nature of the alkynes. In contrast, oxyarylation was observed exclusively when 2-substituted quinoline N -oxides were reacted with 9-ethynylphenanthrene. However, alkynes with electron-withdrawing groups provided only olefination products with 2-substituted quinoline N -oxides. The developed strategy allowed a facile functionalization of quinoline N -oxides bearing natural molecules and an estrone-derived terminal alkyne to deliver the corresponding olefinated and oxyarylated products. To understand the reaction mechanism, control experiments, deuterium-labeling experiments, and kinetic isotope effect (KIE) studies were performed.