Regioselective Catalytic and Stepwise Routes to Bulky, Functional-Group-Appended, and Luminescent 1,2-Azaborinines

The regioselective syntheses of 1,2-azaborinines is achieved using an unsymmetrical iminoborane through both catalytic and stepwise modular routes. The 1,2-azaborinine ring can be selectively functionalized in the 4- and/or 6-position through control of the stepwise reaction sequence, allowing access to vinyl-functionalized and redox-active, luminescent, donor-functionalized 1,2-azaborinines. The electrochemistry and photochemistry of a tetraarylamine-substituted 1,2-azaborinine are studied. Cyclic voltammetry of this compound, relative to a non-B, N-substituted reference molecule, showed an additional oxidation wave assigned to the oxidation of the azaborinine ring, while emission spectroscopy indicated that the azaborinine was significantly more fluorescent than the reference.