Carbene-Assisted Arene Ring-Opening

Zengrui Cheng, Haoran Xu, Zhibin Hu, Minghui Zhu, K. N. Houk*, Xiao-Song Xue*, and Ning Jiao*

J. Am. Chem. Soc. 2024, jacs.4c03634. https://doi.org/10.1021/jacs.4c03634

Abstract

Despite the significant achievements in dearomatization and C–H functionalization of arenes, the arene ring-opening remains a largely unmet challenge and is underdeveloped due to the high bond dissociation energy and strong resonance stabilization energy inherent in aromatic compounds. Herein, we demonstrate a novel carbene assisted strategy for arene ring-opening. The understanding of the mechanism by our DFT calculations will stimulate wide application of bulk arene chemicals for the synthesis of value-added polyconjugated chain molecules. Various aryl azide derivatives now can be directly converted into valuable polyconjugated enynes, avoiding traditional synthesis including multistep unsaturated precursors, poor selectivity control, and subsequent transition-metal catalyzed cross-coupling reactions. The simple conditions required were demonstrated in the late-stage modification of complex molecules and fused ring compounds. This chemistry expands the horizons of carbene chemistry and provides a novel pathway for arene ring-opening.