Late-stage functionalization of BN-heterocycles.

BN/CC isosterism has emerged as a viable strategy to expand the chemical space of organic molecules. In particular, the application of BN/CC isosterism to arenes has received significant attention due to the vast available chemical space provided by aromatic hydrocarbons. The synthetic efforts directed at assembling novel aromatic BN heterocycles have resulted in the discovery of new properties and functions in a variety of fields including biomedical research, medicinal chemistry, materials science, catalysis, and organic synthesis.

1,2-Azaborine's Distinct Electronic Structure Unlocks Two New Regioisomeric Building Blocks via Resolution Chemistry.

Two new 1,2-azaborine building blocks that enable the broad diversification of previously not readily accessible C4 and C5 ring positions of the 1,2-azaborine heterocycle are developed. 1,2-Azaborine's distinct electronic structure allowed the resolution of a mixture of C4- and C5-borylated 1,2-azaborines. The connection between the electronic structure of C4 and C5 positions of 1,2-azaborine and their distinct reactivity patterns is revealed by a combination of reactivity studies and kinetic measurements that are supported by DFT calculations.