Synthesis of Functionalized 1,3,2-Benzodiazaborole Cores Using Bench-Stable Components

The azaborine motif provides a unique opportunity to develop core isosteres by inserting B–N units in place of CC bonds within aromatic scaffolds, creating new pseudoaromatic building blocks that retain comparable structural features. Previous synthetic routes to the 1,3,2-benzodiazaborole core have used organoboron dichlorides and boronic acids as the boron precursors. The transformation developed herein utilizes entirely bench stable starting materials, including organotrifluoroborates, enabling a wider array of substrate analogues under facile reaction conditions. Furthermore, physical, structural, and electronic properties of these compounds were explored computationally to understand the influence of the B–N replacement on the structure, aromaticity, and isosteric viability of these analogues.