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

Abstract

A 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.