Organophosphoric Acid Catalyzed Cyclization–Aromatization of 3-Vinylindoles and 2-Vinylpyridines to Access C3N2 Carbazole–Pyridine Frameworks

Cui Jian; Shushu Xiong; Yong-Ke He; Yu-Ming Yang; Shaoyu Li

doi:10.1055/a-2550-8091

Synlett, Inhaltsverzeichnis

Synlett 2025; 36(14): 2005-2008
DOI: 10.1055/a-2550-8091

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Organophosphoric Acid Catalyzed Cyclization–Aromatization of 3-Vinylindoles and 2-Vinylpyridines to Access C3N2 Carbazole–Pyridine Frameworks

Cui Jian‡

^aCollege of Science, Shenyang University of Chemical Technology, Shenyang 110142, P. R. of China

,

Shushu Xiong‡

^aCollege of Science, Shenyang University of Chemical Technology, Shenyang 110142, P. R. of China

,

Yong-Ke He∗

^aCollege of Science, Shenyang University of Chemical Technology, Shenyang 110142, P. R. of China

,

Yu-Ming Yang∗

^bSchool of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, Taizhou 318000, P. R. of China

,

Shaoyu Li ∗

^bSchool of Pharmaceutical and Chemical Engineering and Institute for Advanced Studies, Taizhou University, Taizhou 318000, P. R. of China

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Abstract

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Abstract

A practical, organophosphoric acid-catalyzed, two-component cyclization–aromatization reaction of 3-vinylindoles with 2-vinylpyridines has been established for the efficient assembly of various functionalized 1-pyridin-2-yl-9H-carbazole skeletons. This transformation involves an organophosphoric acid-catalyzed [4+2] cycloaddition reaction, together with a tandem oxidative aromatization process. This synthetic methodology, characterized by mild reaction conditions, outstanding functional-group tolerance, and a scalable synthesis capability, has the potential to support in-depth explorations in the fields of materials science and biomedicine.

Key words

phosphoric acid catalysis - vinylindoles - vinylpyridines - [4+2] cycloaddition - oxidative aromatization - pyridinylcarbazoles

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Referenzen

References and Notes

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16 CCDC 2349792 contains the supplementary crystallographic data for compound 3a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
17 1-Pyridin-2-ylcarbazoles 3a–x; General Procedure A tube was charged with the appropriate vinylindole 1 (0.1–0.2 mmol, 1.0 equiv), vinylpyridine 2 (0.11–0.22 mmol, 1.1 equiv), catalyst C3 (10–20 mmol%), and chloranil (0.25–0.5 mmol, 2.5 equiv). The tube was then evacuated and refilled three times with N₂. Toluene (2–4 mL) was added, and the mixture was stirred at 40–60 °C for 18–72 h until the reaction was complete (TLC). The mixture was then concentrated under reduced pressure and the residue was purified by column chromatography. Methyl 1-Pyridin-2-yl-9H-carbazole-3-carboxylate (3a) White solid; yield: 93% (0.1 mmol scale) or 94% (5 mmol scale). ¹H NMR (400 MHz, CDCl₃): δ = 11.58 (s, 1 H), 8.72 (s, 1 H), 8.66–8.65 (d, J = 4.4 Hz, 1 H), 8.57 (s, 1 H), 8.06–8.00 (m, 2 H), 7.73–7.69 (m, 1 H), 7.47 (d, J = 8.1 Hz, 1 H), 7.39 (t, J = 7.6 Hz, 1 H), 7.22–7.14 (m, 2 H), 3.91 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 1167.9, 156.89, 148.5, 141.2, 140.2, 136.9, 126.6, 124.6, 124.6, 123.5, 122.9, 121.8, 120.6, 120.6, 120.2, 120.2, 119.4, 111.5, 52.1. HRMS (ESI-ion trap); m/z [M + Na]⁺ calcd for C₁₉H₁₄N₂NaO₂: 325.0953; found: 325.0945.

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