Synlett 2013; 24(12): 1533-1540
DOI: 10.1055/s-0033-1339181
letter
© Georg Thieme Verlag Stuttgart · New York

A One-Pot Stereoselective Synthesis of Electron-Deficient 4-Substituted (E,E)-1-Arylsulfonylbuta-1,3-dienes and Their Chemoselective [3+2] Cycloaddition with Azomethine Ylides – A Simple Synthesis of 1,3,4-Trisubstituted Pyrrolidines and Pyrroles

Ulaganathan Sankar
a   Department of Chemistry, Pachaiyappa’s College, University of Madras, Chennai – 600 030, India
,
Susarla Mahalakshmi
a   Department of Chemistry, Pachaiyappa’s College, University of Madras, Chennai – 600 030, India
,
Kalapattu Kuppuswamy Balasubramanian*
b   Department of Chemistry, B.S. Abdur Rahman University, Chennai – 600 048, India   Email: kkbalu@hotmail.com
› Author Affiliations
Further Information

Publication History

Received: 17 April 2013

Accepted after revision: 13 May 2013

Publication Date:
11 June 2013 (online)


Abstract

A simple and efficient method for the synthesis of (E,E)-1-(arylsulfonyl)buta-1,3-dienes bearing electron-withdrawing substituents like cyano and ethoxycarbonyl at position 4, involving a one-pot alkylation of bis(phenylsulfonyl)methane with trans-ethyl 4-bromocrotonate/trans-4-bromocrotononitrile, and elimination of arylsulfinic acid, is described. These dienes undergo facile mono [3+2] cycloaddition with azomethine ylides chemoselectivity to furnish functionalized 1,3,4-trisubstituted pyrrolidines. Oxidation of these cycloadduct with MnO2·SiO2 under mild conditions provides 1,3,4-trisubstituted pyrroles.

Supporting Information

 
  • References and Notes


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  • 30 General Procedure for the Synthesis of Ethyl 1-tert-Butyl-4-[(E)-2-(phenylsulfonyl)vinyl]-1H-pyrrole-3-carboxylate (10a) Activated MnO2 on silica (13.7 mol, freshly prepared) was added to a stirred solution of ethyl 1-tert-butyl-4-[(E)-2-(phenylsulfonyl)vinyl]pyrrolidine-3-carboxylate (8a, 2.74 mol) in anhyd 1,4-dioxane (20 mL) under argon. After being stirred at reflux for 5 h (monitored by TLC), the reaction mixture was filtered through a pad of Celite, and the pad was washed with 1,4-dioxane. Evaporation of the filtrate under vacuum furnished the crude product, which was subjected to column chromatography (25% EtOAc in n-hexane) to yield analytically pure ethyl 1-tert-butyl-4-[(E)-2-(phenylsulfonyl)-vinyl]-1H-pyrrole-3-carboxylate (10a) as a pale yellow gummy liquid in 68% yield. 1H NMR (400 MHz, CDCl3): δ = 8.02 (d, 1 H, J = 15.4 Hz), 7.93 (m, 2 H), 7.51 (m, 4 H), 7.11 (s, 1 H), 6.98 (d, 1 H, J = 15.4 Hz), 4.26 (q, 2 H), 1.38 (s, 9 H), 1.34 (t, 3 H) ppm. 13C NMR (400 MHz, CDCl3): δ = 164.13, 138.47, 133.73, 133.34, 128.89, 128.73, 125.23, 121.60, 116.08, 116.04, 60.15, 56.78, 30.29, 14.36 ppm. LC–MS (EI): m/z = 384.4 [M+ + Na]. Anal. Calcd for C19H23NO4S: C, 63.13; H, 6.41; S, 8.87; N, 3.88. Found: C, 63.47; H, 6.47; S, 8.52; N, 3.68