Finally, while an excess of tri-topic or di-topic amine was used in the HT screen, the 1 H NMR and mass spectra of the 54 identified cages were manually inspected and interpreted where possible to confirm the identification of the formed cages. Overall, 42 combinations were characterised (see Section S6.1-6.2), with the spectra of the remaining 12 also included in the latter. Those which were more difficult to interpret typically involved precursors with a reduced symmetry compared to their topicity (such as S), or that could form unsymmetrical species (such as P), meaning they passed all of the automated data analysis but often contained either broad peaks or complex splitting on manual inspection. However, perhaps more interestingly, manual inspection also led to the identification of potential competitive reactivity for some precursor combinations. This included precursors 12 and Q which contain α,β-unsaturated aldehydes, where addition of a nucleophile, such as the primary amine precursors used in this screen, have the potential to result in competitive 1,4-vs 1,2-addition. Use of a soft nucleophile, such as a primary amine, has previously been shown to preferentially undergo 1,2addition, yielding products of α,β-unsaturated imines that have been rationalised as the kinetically favoured product. The absence of the aldehyde peak in the automated 1 H NMR analysis follows this suggestion, however, we do acknowledge the potential for this competitive pathway to occur, as tautomerisation to an enol from the 1,4-addition would also lead to the absence of an aldehyde peak and have indicated this in Section S6.1. In addition, we previously reported the potential for competitive aminal formation over imine formation during the synthesis of organic cages, and we believe this was also observed here in combinations containing precursor 18, which may be attributed to the Thorpe-Ingold effect where the gem-dimethyl functionality favours intramolecular cyclisation to the aminal over intermolecular imine formation to form a cage species. When combined with trialdehydes S and U, the ditopic amine precursor 18 passed all of the automated data analysis, with both indicating the formation of a Tri 2 Di 3 topology based on the HRMS analysis. However, on manual inspection of the 1 H NMR spectra, we observed evidence for both cage and aminal formation, further confirmed through identification of the [1+3] aminal-intermediate species in the HRMS spectra (Figures and).