Strategy for Stereoselective Metal‐free α‐Functionalization of 2‐Azaaryl Acetates with N‐Boc Imines

We report the first diastereo- and enantioselective formal Mannich reaction of 2-pyridyl acetates which gives rise to α- and β-functionalized 2-substituted pyridines. Key for success is the previous azaarene N-oxide formation enabling α-carbon deprotonation by a mild bifunctional Bronsted base and subsequent reaction with N-Boc imines under almost perfect stereocontrol.