华东师范大学姜雪峰课团队近日研究了多环芳烃的发散性调控。2025年7月17日出版的《科学通报》杂志发表了这项成果。

Arynes是一种简单有效的π-扩展同时伴随邻域双官能化的合成子，是构建多环芳烃（PAHs）的理想材料。然而，在芳香体系中，C≡C三键，由于键角扭曲和键距缩短，芳香异构对其热力学稳定性和动力学反应选择性提出了巨大的挑战，特别是对杂芳异构。

研究组通过设计的环吡啶-苯λ3-碘烷实现了氮掺杂多环芳烃的可控芳烃生成，其中碘通过与芳烃的p→π*相互作用保证了热力学稳定性和动力学位点选择性，具有化学选择性和区域选择性。“吡啶-苯”模型实现了优异的亲核捕获和连续[4+2]环加成π共轭扩展的正选择性，不仅使N掺杂的多环芳烃具有可调节的分子内扭曲电荷转移（TICT）和反向邻近抑制效应（SOPE）现象，而且为调节芳烃的生成和释放建立了可靠的经验公式。

附：英文原文

Title: Divergent aryne regulation for polycyclic aromatic hydrocarbons

Author: Xiaotian Qi b, Xuefeng Jiang a d e

Issue&Volume: 2025/07/17

Abstract: Arynes are straightforward and effective synthons for π-extension accompanying by vicinal difunctionalization simultaneously, thereby being ideal building blocks for polycyclic aromatic hydrocarbons (PAHs) construction. However, C≡C triple bond in an aromatic system, with the distorted bond angle and shortened bond distance, arouses tremendous challenges for thermodynamic stability and kinetically reactive selectivity, especially for heteroarynes. Herein, controllable aryne generation was achieved for nitrogen-doped polycyclic aromatic hydrocarbons via designed cyclic pyridine–benzene λ3-iodanes, in which the iodine ensured the thermodynamic stability and kinetic site-selectivity via p→π* interaction with aryne for chemo- and regio-selectivity. The “pyridyne–benzyne” model enabled the preeminent ortho-selectivity with nucleophilic capture and consecutive [4+2]-cycloaddition for π conjugation extension, not only assembling for N-doped PAHs with adjustable Twisted Intramolecular Charge Transfer (TICT) and inverse Suppression of Proximity Effect (SOPE) phenomenon but also establishing a reliable empirical formula for regulating generation and release of arynes.

DOI: 10.1016/j.scib.2025.07.026

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927325007492