A method for the synthesis of amide‐containing molecules was developed using vinylazides as an enamine‐type nucleophile towards carbon electrophiles, such as imines, aldehydes, and carbocations that were generated from alcohols in the presence of BF3⋅OEt2. After nucleophilic attack of the vinylazide, a substituent of the resulting iminodiazonium ion intermediate migrates to form a nitrilium ion,