Catalytic Ring Expansion of Cyclic Hemiaminals for the Synthesis of Medium‐Ring Lactams

A mild and efficient intermolecular ring-expansion approach was developed for the synthesis of medium-ring lactams by using siloxy alkynes. Key to success is the suitable combination of a superior catalyst and an exceptional nitrogen-protecting group. Control experiments indicated that the reaction is remarkably selective toward the desired lactam formation, even with many possible non-productive pathways.