Photoredox Catalytic Three-Component Amidoazidation of 1,3-Dienes

In spite of the obvious synthetic potential of functionalized allylic azides, only limited synthetic routes have been developed. We report herein a three-component 1,2-amidoazidation of 1,3-dienes. In the presence of fac-Ir(ppy)(3) under blue LED irradiation, reaction of 1-aryl substituted 1,3-dienes with N-amidopyridinium salt and trimethylsilyl azide (TMSN3) affords exclusively the 1,2-amidoazidation products. The 1-alkyl substituted counterparts undergo the same reaction with moderate to high 1,2- vs 1,4-selectivity. Reduction of this mixture with PPh3 under dynamic kinetic conditions enriches significantly one of the two isomers thanks to the facile 1,3-azide shift (Winstein rearrangement) of the allyl azides.