5-Acyloxymethyl- or 5-phenoxymethyl-2-pyrrolidino-1,4-benzoquinones undergo photocyclization upon exposure to visible light to give an unstable aminophenol photoproduct which eliminates the carboxylate or phenolate leaving groups (LG). For phenolate as leaving group the initial cyclized photoproduct is sufficiently stable with respect to leaving group elimination to be isolated. Its rate of elimination is pH-dependent. The leaving group eliminations afford an ortho-quinone methide intermediate, which can be readily observed by absorption spectroscopy and trapped by beta-aminoalkenones to give cycloadducts. The photochemical step is efficient in intermediate polarity solvents but becomes less efficient with increasing solvent polarity.