A key consideration relevant to this question was whether the configuration at the aminal stereocenter (R vs S) played a role in biasing the terpyridine configuration (M vs P). One of our groups had previously discovered a correlation (R 2 = 0.97) between the dr of 8 and the measured CD signal intensity (Figure ). On the basis of this striking correlation, it was concluded that a point-to-point-to-helix mechanism of stereochemical transfer was operative (Figure ). This can be conceptually deconstructed into two steps: (1) the alcohol stereocenter (highlighted with a blue star) causes one of the hemiaminal ether epimers (stereocenter highlighted with a grey sphere) to be enriched. In turn, the configuration of the aminal influences the energetics to favor one of the two terpyridine configurational twists. It was determined that the (S)-aminal led to (P)-helicity and the (R)-aminal led to (M)-helicity. Therefore, the ratio of aminal epimers directly controls the magnitude of the CD signal. Given the good correlation previously observed between CD signal intensity and dr for assembly 8, we questioned whether a similar relationship existed for the g-stereogenic alcohol-derived assemblies 12 (Figure ). In order to test this, we measured the dr of several assemblies 12a via 1 H-NMR spectroscopy as previous reported. 39,40 Although a similar range of values was observed (dr =1.1 -2.2), there was no correlation with CD signal intensity. This suggested that either: (1) another variable was at play that obscured the correlation, or (2) the hemiaminal ether stereochemistry did not strongly influence the pyridine configuration and, instead, another mechanism for stereochemical transfer was involved.