Mild Stereoselective Intermolecular Acetoxylation and Azidation of α-C−H Bonds in Tröger's Bases

Introduction of oxygen and nitrogen into organic molecules is one of the fundamental strategies for their functionalization. Traditional approaches rely on the formation of an activated intermediate, which is then modified in a subsequent step. Here we report a simple direct oxidative α‐acetoxylation and azidation of α‐C−H bonds in Tröger's base analogues promoted by N‐bromosuccinimide (NBS) and palladium(II)acetate [Pd(OAc)2] under mild conditions. This approach is pivotal on NBS oxidizing the carbon atoms next to the nitrogen atoms in the presence of Pd(OAc)2 followed by a reaction with oxygen‐ or nitrogen‐centred nucleophiles such as KOAc or NaN3 to yield either the mono‐ and bisacetoxylated or azidated Tröger's base derivatives in a stereo‐ and chemoselective manner. The obtained products can be efficiently modified to access synthetically meaningful structures.