Ruthenium-Catalyzed Synthesis of Pyrrolo[1,2-a]quinoxaline Derivatives from 1-(2-Aminophenyl)pyrroles and Sulfoxonium Ylides

Xin-Feng Cui; Fang-Peng Hu; Xiao-Qiang Zhou; Zhen-Zhen Zhan; Guo-Sheng Huang

doi:10.1055/s-0040-1707119

Synlett, Table of Contents

Synlett 2020; 31(12): 1205-1210
DOI: 10.1055/s-0040-1707119

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Ruthenium-Catalyzed Synthesis of Pyrrolo[1,2-a]quinoxaline Derivatives from 1-(2-Aminophenyl)pyrroles and Sulfoxonium Ylides

Xin-Feng Cui

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China Email: hgs@lzu.edu.cn

,

Fang-Peng Hu

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China Email: hgs@lzu.edu.cn

,

Xiao-Qiang Zhou

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China Email: hgs@lzu.edu.cn

^bCollege of Chemistry and Material, Weinan Normal University, Shanxi Province, Weinan 714099, P. R. of China Email: zhouxq2017@163.com

,

Zhen-Zhen Zhan

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China Email: hgs@lzu.edu.cn

,

Guo-Sheng Huang ∗

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Department of Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China Email: hgs@lzu.edu.cn

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Abstract

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Abstract

A ruthenium-catalyzed [5+1] annulation of 1-(2-aminophenyl)pyrroles with α-carbonyl sulfoxonium ylides is reported. This reaction provides a one-step method for synthesizing pyrrolo[1,2-a]quinoxaline derivatives under ambient conditions. The system proceeds with a short reaction time and a high functional-group tolerance. Notably, this divergent protocol tolerates β-keto sulfoxonium ylides and can be applied to α-ester sulfoxonium ylides. A preliminary study was made of the mechanism of the reaction, and a reaction pathway is proposed.

Key words

pyrroloquinoxalines - sulfoxonium ylides - aminophenylpyrroles - ruthenium catalysis - activation–cyclization - [5+1] annulation

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References

References and Notes

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22 Phenyl(pyrrolo[1,2-a]quinoxalin-4-yl)methanone (3aa); Typical Procedure A Schlenk tube (20 mL) equipped with a stirrer bar was charged with 1-(2-aminophenyl)pyrroles (1a; 0.2 mmol, 31.6 mg), sulfoxonium ylide 2a (0.3 mmol, 58.8 mg), [RuCl₂(p-cymene)]₂ (2.5 mol%, 3.1 mg), and AgNTf₂ (20 mol%, 15.5 mg) under an air atmosphere (1 atm). Anhyd ^t AmOH was added, and the mixture was stirred at 100 °C for 12 h, then cooled to r.t. The mixture was filtered through a short Celite pad, and the filtrate was concentrated. The residue was purified by column chromatography [silica gel, PE–EtOAc–CHCl₃ (8:1:1)] to give a yellow solid; yield: 71%. ¹H NMR (300 MHz, CDCl₃): δ = 8.20–8.14 (m, 2 H), 8.04–7.99 (m, 2 H), 7.91 (d, J = 8.2 Hz, 1 H), 7.62 (m, 2 H), 7.49 (m, 3 H), 7.21 (d, J = 4.1 Hz, 1 H), 6.96 (m, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 192.36, 149.90, 135.79, 134.73, 133.55, 131.06, 131.00, 129.40, 128.30, 127.92, 125.43, 124.34, 114.87, 114.72, 113.85, 108.86. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₈H₁₃N₂O: 273.1023; found: 273.0939.

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