summarizes the results with respect to an optimization of the order of the reaction steps and the reaction conditions in detail, highlighting the results of the optimization for compound 15a. First attempts with a variation of the order of the reaction steps resulted in different findings: The alkylation of 2-iodoaniline (9) in a first step results in the formation of a double-alkylated by-product, indicating that alkylation should be conducted after the introduction of the desired electron-withdrawing F-tag. Furthermore, full conversion of the Sonogashira reaction was not achieved if the substrate bore both the F-tag and the R 2 on the nitrogen atom. The optimal order of the reaction steps was therefore found to be: (1) a Sonogashira cross-coupling reaction, (2) an N-acylation, and (3) an N-alkylation. The conditions of the Sonogashira coupling, as well as the acylation reaction, both involved the use of DIPEA as a base and acetonitrile as a solvent, and resulted in a full conversion of the starting material after short time (2-5 hours). Finally, the alkylation reaction in the presence of K2CO3 in refluxing acetonitrile yielded the desired precursor 15a. All other compounds 15 shown in Scheme 2 were synthesized according to the same, optimized pathway in mostly very good yields for the single steps and the whole sequence. DIPEA also turned out to be a well-performing base in the alkylation step and could be used as an organic alternative for K2CO3 except when using iodopropane as a reagent, where it led to diminished yields (see SI Table for the comparison of yields). In our model system, the photoinduced cyclization of the F-tagged aniline derivative 15a under previously reported conditions using [Ir(dtbbpy)(ppy)2]PF6 (5) as a photocatalyst did not lead to any conversion. Other catalysts commonly used in related literature, such as ruthenium complexes and the organic dyes Eosin Y and Rose Bengal, were also examined, but gave no conversion of the starting material. Among all tested catalysts, only [Ir(dF(CF3)ppy)2(dtbpy)]PF6 ( ) was found to convert the starting material, at least to a small extend, under conditions as reported by Zhang et al. (Scheme 3).