The BN- [5]helicenes, 1-X (X = Br or Cl, Scheme 1), were targeted from amine 2. Amine 2 forms amineborane adducts 3-X on addition of BX3, with heating leading to dehydrohalogenation to form aminoboranes 4-X. The use of Dewar's conditions, specifically conversion of 3-Cl to aminoborane 4-Cl, addition of AlCl3 and then heating (up to 175 °C ), led to a complex reaction mixture with no 1-Cl observed (by NMR spectroscopy). Many azaborines are made by addition of excess BBr3 to the amine and heating, 4b, 11 therefore excess BBr3 was added to 3-Br. However, heating under a range of conditions (at temperatures ranging from 85 °C to 150 °C) led to minimal conversion to the azaborine 1-Br even after prolonged reaction times (based on diagnostic resonances in the 1 H and 11 B NMR spectra). Furthermore, heating 4-X/BBr3 at 150°C for prolonged periods actually led to the formation of significant amounts of unidentified by-products and insoluble material. Therefore, these established Ndirected borylation routes do not afford 1-X in any significant yield (all reactions afforded < 30% 1-X by in-situ NMR spectroscopy). Scheme 1. Attempts to form 1-X using previously reported borylation methods.