Functionalization of a Pyridine Framework through Intramolecular Reissert–Henze Reaction of N ‐(Carbamoyloxy)pyridinium Salts and Unexpected Insertion of Ethereal Solvents

A new strategy for synthesis of the 2‐pyridyl carbamates is reported. This strategy exploits a new intramolecular transformation of an acyloxy group from N ‐carbamoyloxypyridinium salts (Reissert–Henze‐type reaction) as the key step. Addition of a silver salt effectively accelerates the intramolecular attack of the carbonyl oxygen at the 2‐position of the pyridine ring. Additionally, a new rearrangement of the acyloxy group, combined with insertion of an ethereal solvent to give pyridine derivatives having a coordinating tether, is reported.