Deprotonation of isoazatruxene enables photocatalytic arylation and phosphorylation of (hetero)aryl halides

Cen Zhou; Xi-Xian Chen; Bohang An; Ling-Wei Wu; Hao Cui; Xiao Zhang

doi:10.1039/d5ob00537j

Deprotonation of isoazatruxene enables photocatalytic arylation and phosphorylation of (hetero)aryl halides

Org Biomol Chem. 2025 Jun 9. doi: 10.1039/d5ob00537j. Online ahead of print.

Authors

Cen Zhou¹, Xi-Xian Chen², Bohang An², Ling-Wei Wu², Hao Cui², Xiao Zhang²

Affiliations

¹ Fujian Engineering and Research Center of New Chinese Lacquer Materials, College of Materials and Chemical Engineering, Minjiang University, Fuzhou 350108, China.
² Fujian Key Laboratory of Polymer Materials, Fujian Provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350117, China. cuihao@fjnu.edu.cn.

PMID: 40488648
DOI: 10.1039/d5ob00537j

Abstract

Isoazatruxene and its derivatives, which can be readily synthesized via cyclotrimerization, have been discovered as novel organic photocatalysts with high catalytic performance. However, the N-unsubstituted isoazatruxene (ITN-1) shows poor absorption in the visible region. Herein, we report that treatment of ITN-1 with Cs₂CO₃ generates the N-centered isoazatruxene anionic species (ITN3-), which exhibits enhanced visible-light absorption and potent reducing ability. Under the photocatalysis of ITN3-, the dehalogenative arylation and phosphorylation of aryl halides can be efficiently achieved, enabling the rapid assembly of pyrrole-containing biaryls and aryl phosphonates. The synthetic utility is further demonstrated by late-stage modification of complex molecules and multi-phosphorylation. Mechanistic studies confirm that the deprotonation of isoazatruxene results in enhanced visible-light absorption and improved photophysical properties.