The unprecedented β-CarOx ligands were conceived by the hybridization of alangiobussinine and the privileged pyridine–oxazoline scaffold. They performed well in the highly enantioselective Pd-catalyzed Michael addition of arylboronic acids to nitrostyrenes and β-substituted cyclic enone (up to 99% ee). The β-CarOx ligands also showed an enhanced antifungal effect compared to alangiobussinine, demonstrating promising antifungal leads against Sclerotinia sclerotiorum.