Abstract
A series of benzylic azido compounds were prepared by the reactions of o-acyl-benzoic acids and -benzamides and pyridine analogues with sodium azide, diphenylphosphoryl azide, and trimethylsilyl azide. Thermal decomposition of the derived benzylic azides afforded three types of rearrangement products. The selectivity of rearrangement depended on the migratory aptitude of substituents and on stereoelectronic factors.

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