Blue Light-Promoted Cross-Coupling of α-Diazo Esters with Isocyanides: Synthesis of Ester-Functionalized Ketenimines.

A metal-free scalable synthesis of functionalized ketenimines from alkyl α-(aryl/heteroaryl)-α-diazoacetates and alkyl isocyanides induced by blue light irradiation has been developed. The reaction proceeds at room temperature without any photocatalyst and provides ketenimines in moderate to good yields. Density functional theory (DFT) calculations and the experimental study showed that aryl(alkoxycarbonyl)carbenes in both singlet and triplet states can react with isocyanides but only the reaction of the former leads to the smooth formation of ketenimines. The obtained ketenimines were used for the synthesis of functionalized amidines under mild metal-free conditions.

Light-induced one-pot synthesis of pyrimidine derivatives from vinyl azides.

A one-pot procedure for the synthesis of tetrasubstituted dihydropyrimidine and pyrimidine derivatives from α-azidocinnamates was developed. The synthesis is based on the finding that the outcome of LED photolysis of α-azidocinnamates depends on the light wavelength employed. Blue light (455 nm) leads to the formation of 2H-azirines only, but violet light (395 nm), UV-A light (365 nm), or sunlight result in the transformation of the in situ formed 2H-azirines to 1,3-diazabicyclo[3.1.0]hex-3-enes. Under basic catalysis (DBU), the latter were isomerized to 1,6-dihydropyrimidines which were oxidized to pyrimidines using DDQ. A successful use of Cs2CO3 as a base and air as an oxidant was also demonstrated.