Cobaloxime‐Based Metalloradical Catalysis: A Versatile Strategy for the Synthesis of Cyclopropenes and Oxazoles

Abstract Metalloradical catalysis (MRC), predominantly exemplified by metalloporphyrin complexes, has emerged as a promising strategy for regulating radical reactions and broadening their synthetic applications. Here, an efficient catalytic method has been devised for the radical [2 + 1] cyclopropenation of alkynes and radical [3 + 2] oxazolation of nitriles using α‐aryldiazoacetates via MRC. Cobaloxime proves effective in facilitating the metalloradical [2 + 1] cyclopropenation of alkynes and radical [3 + 2] oxazolation cycloaddition reaction under mild conditions. The reactions demonstrate broad substrate tolerance, accommodating gram‐scale transformations and the synthesis of pharmaceutical compounds. Our findings highlight the significant potential of cobaloxime‐catalyzed cycloaddition as a valuable tool in organic synthesis and broaden the scope of metalloradical systems in catalysis.