Synlett 2015; 26(08): 1059-1062
DOI: 10.1055/s-0034-1380403
letter
© Georg Thieme Verlag Stuttgart · New York

Zinc and Trimethylsilyl Chloride Mediated Synthesis of 2,3,5-Trisubstituted Pyrrole Diesters from Nitriles and Ethyl Bromoacetate

H. Surya Prakash Rao*
Department of Chemistry, Pondicherry University, Pondicherry 605 014, India   Email: hspr.che@pondiuni.edu.in
,
Avinash Desai
Department of Chemistry, Pondicherry University, Pondicherry 605 014, India   Email: hspr.che@pondiuni.edu.in
› Author Affiliations
Further Information

Publication History

Received: 27 December 2014

Accepted after revision: 27 January 2015

Publication Date:
27 February 2015 (online)


Abstract

An efficient, zinc-mediated, single-pot and CN+3C type pseudo-four-component synthesis of 2,3,5-trisubstituted pyrrole diesters was achieved from readily available aromatic/benzylic/aliphatic nitriles and ethyl bromoacetate under trimethylsilyl chloride catalysis.

Supporting Information

 
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  • 26 Synthesis of Ethyl 5-(2-Ethoxy-2-oxoethyl)-2-phenyl-1H-pyrrole-3-carboxylate (2a); Typical Procedure: To a slurry of zinc powder (0.96 g, 9.94 mmol) in anhydrous THF (6 mL) under a nitrogen atmosphere, TMSCl (0.26 g, 50 mol% in 1 mL THF) was added and the resulting suspension was heated to reflux for 20 min. To this refluxing slurry of activated zinc, benzonitrile 1a (0.51 g, 4.97 mmol in 1 mL THF) and ethyl bromoacetate (2.51 g, 17.91 mmol) were added simultaneously by using two syringes. Soon after initial addition of the two reactants the reaction mixture became dark green and finally red. The reaction mixture was heated to reflux for 6 h to achieve completion (TLC; EtOAc–hexanes, 20%; Rf = 0.3). The THF was removed under reduced pressure and the resulting mixture was subjected to silica gel column chromatography (EtOAc–hexanes, 20%) to afford 2a (1.35 g, 91%) as a pale-yellow viscous liquid. IR (KBr): 3334, 2930, 2858, 1738, 1702, 1675, 1223, 781 cm–1. 1H NMR [400 MHz, CDCl3 + CCl4 (1:1)]: δ = 9.48 (s, 1 H), 7.50–7.52 (m, 2 H), 7.26–7.30 (m, 3 H), 6.46–6.46 (d, J = 2 Hz, 1 H), 4.08–4.14 (m, 4 H), 3.55 (s, 2 H), 1.19–1.27 (m, 6 H). 13C NMR [100 MHz, CCl4 + CDCl3 (1:1)]: δ = 170.7 (C), 164.9 (C), 137.1 (C), 129.1 (2CH), 127.8 (2CH), 123.5 (C), 111.9 (C), 111.1 (CH), 61.1 (CH2), 59.4 (CH2), 32.7 (CH2), 14.2 (CH3), 14.1 (CH3). HRMS (ESI): m/z [M + Na]+ calcd for C16H14N2O3Na: 305.0902; found: 305.0900.