Enaminones are an important class of synthetic building blocks with intriguing both ambident eletrophilicity of enones (Cα and carbonyl C) and ambident nucleophilicity of enamines (N and Cβ). These versatile synthons have been used for transition-metal-catalyzed, directed C-H bond functionalization and cyclization reactions. The cyclization reactions reported thus far are restricted to C-C bond formation at the Cβ (dominant site, through its nucleophilicity) and Cα (minor site, through C-H bond activation). Herein an intriguing mode of C-N bond formation at the carbonyl C site has been identified in coupling with oxadiazolones, accompanied by a unique Cβcarbonyl C bond cleavage. The quinazolinone skeleton generated hereof has proven their privileged pharmacore role in an extensive spectrum of disease settings. They have been harnessed as anti-bacterial, anti-fungal, anti-HIV, anti-malaria, anti-diabetes (ghrelin receptor antagonist), anticonvulsant, anti-inflammatory, anti-cancer (tyrosine kinase inhibitor), and analgesic agents. Although a variety of methods have been invented for the construction of this molecular scaffold, requirement of multiple steps for functional group installation, reliance on rare metal catalysts, and restriction in substrate scope enormously limited their synthetic utility (Scheme 2). The combination of a base metal cobalt catalyst with conveniently accessible and bench-stable enaminones and oxadiazolones will revamp the synthetic logic of the field.