Irradiation of diazirine 30 in methanol at 350 nm for 15 minutes led to the predominant formation of alkene 31 with the only minor formation of the needed O-H insertion products 32 and 33 (Scheme 4). At 310 nm, the formation of 13% of the needed insertion product 31 was already observed. Both compounds 31 and 32 were isolated and fully characterized to additionally confirm their structure that was originally proposed based on LC-MS data. Irradiation of diazirine 30 in the acetonitrile-water mixture (9:1) at 310 nm already gave a significant amount of the needed O-H insertion product 33. Moreover, irradiation at 350 nm provided >40% of insertion products 33 and 34 (via Ritter-type reaction). The latter experiment clearly demonstrated the full compatibility of the aliphatic trifluoromethyl diazirine motif with photoaffinity experiments.