Reactivity of Glutaconamides Within [2]Rotaxanes: Mechanical Bond Controlled Chemoselective Synthesis of Highly Reactive α‐Ketoamides and their Light‐Triggered Cyclization

Abstract

AbstractGlutaconamide‐based [2]rotaxanes are efficiently oxidized to the respective interlocked α‐ketoamides, whereas their non‐interlocked threads afford hydroxycyclohexene tetraamides under similar reaction conditions. These results showcase the mechanically interlocking of highly reactive substrates as a powerful tool for controlling their chemical behavior. Inside the macrocycle and under irradiation with light, the α‐ketoamide threads convert, in a divergent manner, into the corresponding interlocked hydroxy‐β‐lactams or oxazolidinones by two modes of Norrish/Yang type‐II intramolecular cyclizations, processes that are efficiently chemocontrolled by the mechanical bond.