Synthesis and Reactions of 4‐Azido‐3‐methyl‐1,2‐butadiene

The coupling of an allene system with an azido group via one carbon atom has been achieved for the first time in the synthesis of 1. 1 rearranges to the isomer 2 already at room temperature. In the photolytic decomposition, 1 behaves as a typical azide with an allyl structure, whereas the vinyl azide 2 leads to the azirine 3 in good yield.