Surprising secondary photochemical reactions observed on conventional photolysis of diazotetrahydrofuranones

The formation of C–H insertion products of the terminal N-atom of a diazo group into the α-СН-bond of tetrahydrofuran during direct photolysis of regioisomeric 2,2-dimethyl-5,5-diphenyl and 5,5-dimethyl-2,2-diphenyl-substituted 3-diazotetrahydrofuran-4-ones in THF is dictated by photochemical cycloelimination of the originally formed (1,1-dimethyl-2-oxa-3,3-diphenyl-propano)ketene and oxetanecarboxylic acid derivatives to yield benzophenone. The latter, under subsequent UV irradiation of the reaction mixture, initiates sensitized photolysis of the starting diazoketones resulting in the appearance of the insertion products with the solvent.