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Synlett 2020; 31(12): 1205-1210
DOI: 10.1055/s-0040-1707119
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© Georg Thieme Verlag Stuttgart · New York

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

Xin-Feng Cui
a   State 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
a   State 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 
a   State 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
b   College of Chemistry and Material, Weinan Normal University, Shanxi Province, Weinan 714099, P. R. of China   Email: zhouxq2017@163.com
,
Zhen-Zhen Zhan
a   State 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  ∗
a   State 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
› Author Affiliations
Further Information

Publication History

Received: 07 March 2020

Accepted after revision: 16 April 2020

Publication Date:
12 May 2020 (online)

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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707119.
  • Supporting Information
 

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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.