A new route to azocines and benzoazocines from furopyridinones is described through a photochemically induced [1,3]-sigmatropic rearrangement. The method gives access to these 8-membered nitrogen heterocycles from dimethyl squarate in four stages and with excellent atom economy by sequencing thermal and photochemical ring expansion steps under continuous flow.
A photochemical ring expansion of 6- to 8-membered nitrogen heterocycles by [1,3]-sigmatropic rearrangement.