Copper(I) Iodide Catalyzed Tandem Reactions of N-Propargyl-N-(2-iodoaryl)amides with Sodium Azide: An Efficient Synthesis of [1,2,3]Triazolo[1,5-a]quinoxalines

Abstract

Copper-catalyzed reactions of N-propargyl-N-(2-iodoaryl)amides with sodium azide have been developed, providing a novel and efficient method for the synthesis of [1,2,3]triazolo[1,5-a]quinoxaline compounds under mild conditions in moderate yields by tandem copper-catalyzed azide-alkyne cycloaddition and Ullmann-type coupling.

Key words

tandem reaction - copper catalysis - triazoloquinoxalines - azide–alkyne cycloaddition - Ullmann coupling - click chemistry

Publication History

Received: 29 December 2020

Accepted after revision: 01 February 2021

Article published online:
26 February 2021

• References and Notes

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• 9 [1,2,3]Triazolo[1,5-a]quinoxalines 2a–m; General Procedure The appropriate N-propargyl-N-(2-iodoaryl)amide 1 (0.5 mmol), NaN₃ (0.6 mmol), CuI (0.05 mmol), N,N′-dimethylethylenediamine (0.1 mmol), i-Pr₂NEt (0.5 mmol), and DMF (4 mL) were added to a Schlenk tube at r.t. under N₂, and the mixture was stirred at 50 °C until the reaction was complete (TLC). The solvent was then evaporated under reduced pressure, and sat. aq NH₄Cl was added. The aqueous layer was extracted with CH₂Cl₂ (3 × 20 mL), and the extracts were dried (MgSO₄), filtered, and concentrated in vacuo. The residue was purified with flash chromatography [silica gel, PE–EtOAc (20:1)]. 8-Methyl-3,4-diphenyl-[1,2,3]triazolo[1,5-a]quinoxaline (2a) White solid; yield: 145 mg (86%); mp 193−195 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.61 (s, 1 H), 8.11 (d, J = 8.3 Hz, 1 H), 7.58 (dd, J ₁ = 8.3, J ₂ = 1.5 Hz, 1 H), 7.46−7.44 (m, 2 H), 7.37−7.34 (m, 1 H), 7.29−7.26 (m, 1 H), 7.24−7.16 (m, 6 H), 2.69 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 152.88, 143.72, 141.00, 136.27, 134.77, 130.46, 130.40, 129.93, 129.88, 129.64, 129.01, 128.24, 128.10, 127.79, 125.04, 122.67, 115.32, 21.99. HRMS-ESI; m/z [M + H]⁺ calcd for C₂₂H₁₇N₄: 337.1448; found: 337.1452.
• 10 Li D, Mao T, Huang J, Zhu Q. Chem. Commun. 2017; 53: 1305