Synlett 2014; 25(14): 2036-2038
DOI: 10.1055/s-0034-1378378
letter
© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Tandem Synthesis of Pentasubstituted Pyridines from Sulfonoketenimides and 2-Aminoprop-1-ene-1,1,3-tricarbonitrile

Issa Yavari*
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, 18716 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Zohreh Taheri
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, 18716 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Manijeh Nematpour
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, 18716 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Azam Sheikhi
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, 18716 Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 27 April 2014

Accepted after revision: 30 May 2014

Publication Date:
04 August 2014 (online)


Abstract

Fully substituted pyridines were synthesized in moderate to good yields in a one-pot process by the copper-catalyzed sequential reaction of sulfonyl azides with terminal alkynes and 2-aminoprop-1-ene-1,1,3-tricarbonitrile at room temperature.

Supporting Information

 
  • References and Notes

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  • 10 N-[4-Amino-5-cyano-6-(cyanomethyl)-3-(alkyl/aryl)pyridin-2-yl]-4-(alkyl/aryl)sulfonamides; General Procedure The tetracyano compound 4 was prepared by self-condensation of malononitrile (2 mmol) in CH2Cl2 containing NaH (1 equiv) at r.t. for 30 min. A mixture of sulfonyl azide 2 (1.2 mmol), alkyne 1 (1 mmol), CuI (10 mmol%), and Et3N (1 mmol) in CH2Cl2 (3 mL) was slowly added. The mixture was stirred at r.t. under N2 for about 3 h until the reaction was complete [TLC; EtOAc–hexane (1:5)]. The mixture was then diluted with CH2Cl2 (2 mL) and aq NH4Cl (3 mL), and stirred for 10 min. The layers separated and the aqueous layer was extracted with CH2Cl2 (3 × 3 mL). The organic fractions were combined, dried (Na2SO4), filtered, and concentrated under reduced pressure to give a residue that was purified by flash column chromatography [silica gel (230–400 mesh; Merck), hexane–EtOAc (5:1)]. N-[4-Amino-5-cyano-6-(cyanomethyl)-3-phenylpyridin-2-yl]-4-methylbenzenesulfonamide (5a) Cream powder; yield: 0.34 g (85%); mp 147–149 °C. IR (KBr): 3345, 3106, 2127, 1534, 1399, 1192, 1036 cm–1; 1H NMR (500 MHz, CDCl3): δ = 2.54 (s, 3 H, Me), 4.33 (s, 2 H, s, CH2), 5.78 (s, 2 H, NH2) 7.30–7.35 (m, 3 H, Ph), 7.67 (d, 3 J = 7.4 Hz, 2 H, Ar), 7.70 (d, 3 J = 7.8 Hz, 2 H, Ar), 8.24 (d, 3 J = 7.8 Hz, 2 H, Ar), 8.62 (s, 1 H, NH). 13C NMR (125.7 MHz, CDCl3): δ = 24.4 (CH2), 29.3 (Me), 116.9 (CN), 117.8 (CN), 119.0 (C), 122.5 (C), 124.9 (C), 127.0 (2 CH), 128.9 (2 CH), 130.0 (C), 131.8 (2 CH), 132.4 (2 CH), 135.6 (CH), 145.8 (C), 148.1 (C), 153.1 (C), 159.0 (C). EI-MS: m/z (%) = 403 [M+] (4), 337 (18), 233 (28), 170 (71), 156 (100), 91 (57), 77 (30). Anal. Calcd for C21H17N5O2S (403.46): C, 62.52; H, 4.25; N, 17.36. Found: C, 63.03; H, 4.22; N, 17.52.
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