Intramolecular Borylation via Sequential B−Mes Bond Cleavage for the Divergent Synthesis of B,N,B‐Doped Benzo[4]helicenes

New symmetric and unsymmetric B,N,B-doped benzo[4]helicenes 3-6 a/b have been achieved in good yields, using a three-step process, starting from N(tolyl)₃ in a highly divergent manner (7 examples). A borinic acid functionalized 1,4-B,N-anthracene 1 was found to display unprecedented reactivity, acting as a convenient and highly effective precursor for selective formation of bromo-substituted B,N,B-benzo[4]helicenes 2 a/2 b via intramolecular borylation and sequential B-Mes bond cleavage in the presence of BBr₃ . Subsequent reaction of 2 a/2 b with Ar-Li provided a highly effective toolbox for the preparation of symmetrically/unsymmetrically functionalized B,N,B-helicenes. Their high photoluminescence quantum yields along with the small ΔEST suggest their potential as thermally activated delayed fluorescence (TADF) emitters for organic light-emitting diodes (OLEDs).