Carbene-Assisted Arene Ring-Opening

• Published in: Journal of the American Chemical Society 2024-06, Vol.146 (25), p.16963-16970
• Main Authors: Cheng, Zengrui, Xu, Haoran, Hu, Zhibin, Zhu, Minghui, Houk, K. N., Xue, Xiao-Song, Jiao, Ning
• Format: Article
• Language: English
• Subjects: aromatic hydrocarbons; azides; carbenes; carbon-hydrogen bond activation; cross-coupling reactions; dissociation; energy; value added
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.4c03634

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.