Copper(II)-Promoted Oxidation/[3+2]Cycloaddition/Aromatization Cascade: Efficient Synthesis of Tetrasubstituted NH-Pyrrole from Chalcones and Iminodiacetates

Zhang-qi Lin; Chao-dong Li; Zi-chun Zhou; Shuai Xue; Jian-rong Gao; Qing Ye; Yu-jin Li

doi:10.1055/s-0039-1689972

Synlett, Table of Contents

Synlett 2019; 30(12): 1442-1446
DOI: 10.1055/s-0039-1689972

letter

Copper(II)-Promoted Oxidation/[3+2]Cycloaddition/Aromatization Cascade: Efficient Synthesis of Tetrasubstituted NH-Pyrrole from Chalcones and Iminodiacetates

Authors

Zhang-qi Lin
Chao-dong Li
Zi-chun Zhou
Shuai Xue
Jian-rong Gao
Qing Ye
Yu-jin Li*

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: lyjzjut@zjut.edu.cn

Abstract

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Abstract

A simple and highly efficient method for the preparation of tetrasubstituted NH-pyrrole from a wide range of chalcones and diethyl iminodiacetates via a Cu(OAc)₂-promoted oxidation/[3+2]cycloaddition/aromatization cascade reaction has been developed. This reaction proceeds through dehydrogenations, deamination, and oxidative cyclization, affording the corresponding products in good to excellent yields. This convenient methodology for constructing tetrasubstituted NH-pyrroles has several advantages over existing methods, such as the use of easily accessible chalcones and readily available diethyl iminodiacetates, and mild reaction conditions. A wide range of substrates are tolerated.

Key words

Cu(II)-promoted - tetrasubstituted NH-pyrrole - iminodiacetate - oxidation/[3+2] cycloaddition/aromatization - cascade reaction

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References

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18 All chemicals were purchased from commercial vendors and were used as received without further purification. The ¹H and ¹³C NMR spectra were recorded at 500 and 125 MHz, respectively, in CDCl₃ using TMS as internal standard with a Bruker AM 500 spectrometer. Chemical shifts (δ) are reported as parts per million (ppm) and the following abbreviations are used to identify the multiplicities: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, b=broad and all combinations thereof can be explained by their integral parts. HRMS data were obtained with a Thermo Scientific LTQ Orbitrap XL mass spectrometer and the GC-MS were recorded with an Agilent (GC431-MS210). Thin-layer chromatography was performed on pre-coated glass-backed plates and visualized with UV light at 254 nm. Flash column chromatography was performed on silica gel (see the Supporting Information). Synthesis of 3a; Typical Procedure A mixture of chalcone 1a (0.25 mmol, 0.0520 g), diethyl iminodiacetate 2a (0.5 mmol, 0.0945 g), Et₃N (0.25 mmol, 0.0253 g), and Cu(OAc)₂ (0.25 mmol, 0.0498 g) was dissolved in DMF (1.0 mL) in a thick-walled tube (10 mL). The mixture was stirred at 100 °C for 8 h under air atmosphere, and the progress of the reaction was monitored by TLC (PE/EtOAc = 2:1 (v/v)). Upon completion, the mixture was cooled to r.t. and poured into saturated aqueous NaCl (10.0 mL) and extracted with EtOAc (3 × 10.0 mL). The acquired organic phases were combined and dried over anhydrous Na₂SO₄. After removing the volatile solvent, the product 3a was obtained as a white solid in 90% yield by isolation with silica column chromatography (eluting solvent: petroleum ether/EtOAc = 2:1 (v/v)).

Supplementary Material

Supporting Information (PDF) (opens in new window)