A Golden Synthetic Approach to 2-(1H-Pyrrol-1-yl)anilines and Pyrrolo[1,2-a]quinoxalines through a Gold Carbene Intermediate

Volkan Tasdemir; Hasan Genç; Nurettin Menges

doi:10.1055/a-2159-9400

Synlett, Table of Contents

Synlett 2024; 35(07): 801-806
DOI: 10.1055/a-2159-9400

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A Golden Synthetic Approach to 2-(1H-Pyrrol-1-yl)anilines and Pyrrolo[1,2-a]quinoxalines through a Gold Carbene Intermediate

Volkan Tasdemir

^aMuradiye Vacational School, Van Yüzüncü Yil University, Van, Türkiye

,

Hasan Genç

^bFaculty of Educational Sciences, Van Yüzüncü Yil University, Van, Türkiye

,

Nurettin Menges ∗

^cPharmaceutical Chemistry Section, Van Yüzüncü Yil University, Van, Türkiye

^dEngineering Faculty, Biomedical Engineering, Necmettin Erbakan University, 42100, Konya, Türkiye

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Abstract

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Abstract

The pyrrolo[1,2-a]quinoxaline skeleton has significant potential for many biological and optical applications. Hence, in this study, unconjugated ynone derivatives were treated with 1,2-diaminoarenes in a gold-catalyzed cyclization to give 2-(1H-pyrrol-1-yl)anilines, which are valuable starting materials, and pyrrolo[1,2-a]quinoxalines by a one-pot and single-step approach. A reaction mechanism for the formation of the pyrrolo[1,2-a]quinoxaline skeleton featuring a key gold carbene intermediate is proposed. On the other hand, the methyl group on the C-2 position of the 2-(1H-pyrrol-1-yl)anilines was oxidized by SeO₂ to give the pyrrolo[1,2-a]quinoxaline skeleton, resulting in 14 different pyrrolo[1,2-a]quinoxaline derivatives.

Keywords

pyrroloquinoxalines - diaminoarenes - pyrrolylanilines - gold catalysis - cyclization - oxidation

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References

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19 Pyrrolo[1,2-a]quinoxalines 3; General Procedure with SeO₂ A solution of the appropriate compound 4 (1 mmol) in 1,4-dioxane (5 mL) was refluxed with SeO₂ (3 mmol) in a reaction flask for 24 hours until the reaction was complete (TLC). The solvent was removed by filtration, and the crude product was purified by column chromatography [silica gel, EtOAc–hexane (1:5)]. Methyl 1-Methylpyrrolo[1,2-a]quinoxaline-2-carboxylate (3a) Whie solid; yield: 0.093 g (95%); mp 158–159 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.69 (s, 1 H, –CH), 8.35–3-8.31 (m, 1 H, Ar-H), 7.97–7.93 (m, 1 H, Ar-H), 7.51–7.46 (m, 2 H, Ar-H), 7.26 (d, J = 1.9 Hz, 1 H, pyrrole), 3.90 (s, 3 H, –OCH₃), 3.27 (s, 3 H, –CH₃). ¹³C NMR (100 MHz, CDCl₃): δ = 165.4, 146.7, 137.7, 133.7, 130.3, 129.9, 127.3, 125.9, 125.7, 117.3, 116.4, 109.0, 51.5, 15.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₁₃N₂O₂: 241.09715; found: 241.09769.
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