This study provides a practical route to synthesize tetrasubstituted alkenes that involves Co(III)-catalyzed C-H bond activation and regioselective insertion of the alkyne, followed by chelation of the substrate hydroxyl to Co and migration of the pyridine group. Density functional theory studies revealed the origin of regioselectivity and elucidated the crucial role of the hydroxyl group for the migration of pyridine. The method can be conducted on a gram scale, is compatible with a wide range of substrates, and has a high functional group tolerance. To demonstrate its significance, the method was used for the late-stage modification of Fasudil. Furthermore, the synthetic significance of the method was demonstrated by the various derivatizations of the products, many of which exhibit intriguing fluorescence characteristics.