Tracking the Process of Domino Ring‐Opening and Coupling of Fused Imidazole and Direct Observation of Peroxide Intermediates

Author:

Wang Yu1,Luo Mei‐Lian1,Cai Jin1,Zhang Tao1,Wu Yu‐Jie1,Song Ming‐Da1,Liu Bin1,Zeng Ming‐Hua123

Affiliation:

1. Organic Functional Molecules, College of Chemistry & Chemical Engineering Hubei University Wuhan Hubei 430062 China

2. State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences Guangxi Normal University Guilin Guangxi 541004 China

3. College of Chemistry and Chemical Engineering Jinggangshan University Ji'an Jiangxi 343000 China

Abstract

Comprehensive SummaryA domino ring‐opening and coupling of imidazolyl annulated heterocycles 1 (1a: 4‐methyl‐1‐(1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)‐4H‐ benzo[d]imidazo[1,5‐a]imidazole, 1b: 1‐(1,5‐dimethyl‐1H‐benzo[d]imidazol‐2‐yl)‐4,7‐dimethyl‐4H‐benzo[d]imidazo[1,5‐a]imidazole) with dioxygen was developed at solvothermal condition, leading to conjugated 1,2‐diamidoalkenes derivatives 2 ((E)‐ArCONHArC=CArNHCOAr (Ar: 1‐methyl‐1H‐benzo[d]imidazolyl (2a), 1,5‐dimethyl‐1H‐benzo[d]imidazolyl (2b))) as single crystals directly. The reaction process was tracked by electrospray ionization mass spectrometry (ESI‐HRMS) and a series of reaction intermediates are detected. 18O2 labeling experiment verified the source of oxygen in 2. Combining evidence from control experiments, nuclear magnetic resonance (NMR) tracking, and crystallography, a seven‐step reaction pathway involving oxygen addition, ring opening, Friedel‐Crafts alkylation, oxidation, and dehydration was proposed and further supported by DFT calculation.

Funder

National Natural Science Foundation of China

Publisher

Wiley

Subject

General Chemistry

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