Protonation of aminoboranes by HNTf2 represents a new route to effect N-directed C-H borylation for accessing azaborines. In the systems studied herein it provides better outcomes than that achieved by the more established synthetic approach -activating aminoboranes with BBr3 and heating. This is attributed to the greater electrophilicity of borenium cations generated by aminoborane protonation relative to borenium cation equivalents generated by BBr3 coordination to N of the aminoborane. This HNTf2 mediated C-H borylation methodology thus enables access to azaborines otherwise challenging to access. This includes BN- [5] and [6]helicenes where the BN unit is located on the outer helix. BN incorporation slightly increases the strain present in these helicenes relative to all carbon analogues, but more notably it significantly enhances the photophysical properties ( and F), as observed previously for BN- [4]helicenes, 4 while the absorption anisotropy factor (gabs) for a BN- [6]helicene is comparable to carbohelicene analogues. This work provides an example of BN incorporation into (configurationally stable) helically chiral organic frameworks leading to superior properties relative to all-carbon analogues along with a novel synthetic methodology that will facilitate access to azaborine materials.