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

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

• 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.