*3.9. ORCA MS<sup>2</sup> Auxiliary Pipeline*

Code, data files, and supporting documentation on the use and workings of the ORCA MS<sup>2</sup> Auxiliary pipeline are available at https://github.com/c-leber/ORCA. MS2 spectra were binned with the bin\_OOM parameter set to 0, and the cutoff parameter for the hierarchical clustering of the MS<sup>2</sup> scans for a particular precursor mass was set to 0.15. The MS<sup>2</sup> scans were filtered to only include scans for precursor masses, which contained fragment peaks with *m*/*z* 168, resulting in 78 precursor masses. These precursor masses were individually analyzed via the hierarchical clustering of scan fragmentation patterns followed by the generation of consensus spectra for each cluster. Consensus spectra were manually inspected to detect interpretable fragmentation patterns similar to those of compound **1**.
