Organic azides have shown versatile reactivity to induce various organic transformations for the synthesis of nitrogencontaining organic molecules such as 1,3-dipolar cycloadditions with unsaturated bonds, the Curtius rearrangement,and formation of nitrogen-centered radicals, most of which are driven by the entropic loss of molecular dinitrogen [1].Among organic azides, vinyl azides have shown unique reactivities.Their propensity for the denitrogenative formation of 2H-aziridines via vinyl nitrene intermediates under thermal treatment, photoirradiation or Lewis acidic reaction conditions has been known for long, and it has classically been utilized in the Hemetsburger-Knittel indole synthesis.On the other hand, recent studies have shown that vinyl azides serve as either radical acceptors or as enamine-type nucleophiles, enhancing synthetic capability with the development of novel synthetic transformations (Figure 1(A))[2].