Orienting Group Directed Cascade Borylation for Efficient One‐Shot Synthesis of 1,4‐BN‐Doped Polycyclic Aromatic Hydrocarbons as Narrowband Organic Emitters

1,4‐BN‐doped polycyclic aromatic hydrocarbons (PAHs) have emerged as very promising emitters in organic light‐emitting diodes (OLEDs) due to their narrowband emission spectra that may find application in high‐definition displays. While considerable research has focused on investigating the properties of these materials, less attention has been placed on their synthetic methodology. Here we developed an efficient synthetic method for 1,4‐BN‐doped PAHs, which enables sustainable production of narrowband organic emitting materials. By strategically introducing substituents, such as methyl, tert‐butyl, phenyl, and chloride, at the C5 position of the 1,3‐benzenediamine substrates, we achieved remarkable regioselective borylation in the para‐position of the substituted moiety. This approach facilitated the synthesis of a diverse range of 1,4‐BN‐doped PAHs emitters with good yields and exceptional regioselectivity. The synthetic method demonstrated excellent scalability for large‐scale production and enabled late‐stage transformation of the borylated products. Mechanistic investigations provided valuable insights into the pivotal roles of electron effect and steric hindrance effect in achieving highly efficient regioselective borylation. Moreover, the outstanding device performance of the synthesized compounds 10 b and 6 z, underscores the practicality and significance of the developed method. A series of 1,4‐BN‐doped polycyclic aromatic hydrocarbons were synthesized from triarylamines by orienting group directed regioselective one‐shot cascade borylation. The facile and scalable method enabled sustainable production of diverse organic emitting materials exhibiting narrowband emission. OLEDs based on the emitters showed high color purity in blue and green region with high external quantum efficiencies up to 40.1 %.