A Modular Cascade Synthetic Strategy Toward Structurally Constrained Boron‐Doped Polycyclic Aromatic Hydrocarbons

Abstract

AbstractA novel synthetic strategy was developed for the construction of difficult‐to‐access structurally constrained boron‐doped polycyclic aromatic hydrocarbons (sc‐B‐PAHs) via a cascade reaction from the readily available ortho‐aryl‐substituted diarylalkynes. This domino process involves borylative cyclization, 1,4‐boron migration and successive two‐fold electrophilic borylation. Two types of sc‐B‐PAHs bearing B‐doped [4]helicene (1 a‐1 i) or BN‐doped [4]helicene (1 n‐1 t) and double [4]helicene (1 u‐1 v) are constructed by this cascade reaction. Remarkably, this synthetic strategy is characterized by modest yields (20–50 %) and broad substrate scope (18 examples) with versatile functional group tolerance. The resultant sc‐B‐PAHs show good stability under ambient conditions and are thoroughly investigated by X‐ray crystallography, UV/Vis absorption and fluorescence spectroscopy, and cyclic voltammetry. Interestingly enough, BN‐doped [4]helicene 1 o forms a unique alternating π‐stacked dimer of enantiomers within a helical columnar superstructure, while BN‐doped double [4]helicene 1 u establishes an unprecedented π‐stacked trimeric sandwich structure with a rare 2D lamellar π‐stacking. The synthetic approach reported herein represents a powerful tool for the rapid generation of novel sc‐B‐PAHs, which are highly attractive for the elucidation of the structure‐property relationship and for potential optoelectronic applications.