Interestingly, the photoinduced cyclization of the F-tagged substrate did not yield the expected product. Instead, a rearrangement of the fluorous acyl moiety to the compound 17a was observed (Scheme 3). The 1,3-acyl shift in the cyclization of alkynylated anilines to form 3-acylindoles was reported in literature but could so far, to the best of our knowledge, only be achieved thermally in the presence of metals like platinum, zinc and palladium , like exemplarily shown on Scheme 1b for the platinum catalysed cyclization of 7 to the 3-acylindole derivative 8. Scheme 3. Synthesis of the 3-acylated indole derivative via photochemically induced 1,3acyl shift of the perfluorinated acyl group.