Reaction between Isocyanides,
Dialkyl Acetylenedicarboxylates and 2-Hydroxy-1-aryl-2-(arylamino)ethanones:
One-Pot Synthesis of Highly Functionalized 2-Aminofurans

Mohammad Hossein Mosslemin; Mohammad Anary-Abbasinejad; Hossein Anaraki-Ardakani

doi:10.1055/s-0029-1217951

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Synlett 2009(16): 2676-2678
DOI: 10.1055/s-0029-1217951

LETTER

Reaction between Isocyanides, Dialkyl Acetylenedicarboxylates and 2-Hydroxy-1-aryl-2-(arylamino)ethanones: One-Pot Synthesis of Highly Functionalized 2-Aminofurans

Mohammad Hossein Mosslemin, Mohammad Anary-Abbasinejad*, Hossein Anaraki-Ardakani
Department of Chemistry, Islamic Azad University, Yazd Branch, P.O. Box 89195-155, Yazd, Iran
Fax: +98(351)8211109; e-Mail: mohammadanary@yahoo.com;

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Publication History

Received 26 May 2009
Publication Date:
04 September 2009 (online)

Abstract
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Abstract

A facile synthesis of highly functionalized 2-aminofuran derivatives by the multicomponent reaction of alkyl isocyanides, dialkyl acetylenedicarboxylates and 2-hydroxy-1-aryl-2-(arylamino)ethanone is described. The reaction is characterized by mild conditions, high selectivity, and tolerance to various functional groups.

Key words

alkyl isocyanide - dialkyl acetylenedicarboxylate - multicomponent reaction - 2-aminofuran

References and Notes

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23

Synthesis of 3a as a Typical Route for the Preparation of 2-Hydroxy-1-aryl-2-(arylamino)ethanone Derivatives:
A solution of 4-nitroaniline (10 mmol) and 4-nitrophenyl-glyoxal monohydrate (10 mmol) in EtOH (20 mL) was refluxed for 3 h. The solution was cooled in ice-water bath. The precipitate was filtered of to afford pure 3a as yellow crystals; mp 150-151 ˚C. IR (KBr): 3645 (OH), 3390 (NH), 1690 (C=O) cm^-¹. MS (%): m/z = 317 (7) [M⁺]. Anal. Calcd for C₁₄H₁₁N₃O₆ ₍317): C, 53.00; H, 3.49; N, 13.24. Found: C, 53.12; H, 3.52; N, 13.08. ^¹H NMR (500.1 MHz, CDCl₃): δ = 5.96 (d, ^³ J _HH = 6.5 Hz, 1 H, CH), 6.64 (d, ^³ J _HH = 6.5 Hz, 1 H, NH), 6.84 (d, ^³ J _HH = 9.0 Hz, 2 H, 2 × CH of Ar), 7.96 (d, ^³ J _HH = 9.0 Hz, 2 H, 2 × CH of Ar), 8.18 (d, ^³ J _HH = 8.7 Hz, 2 H, 2 × CH of Ar), 8.23 (d, ^³ J _HH = 8.7 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 81.92 (CHN), 113.56, 124.20, 126.33, 131.12, 138.47, 140.14, 151.08, 151.13 (C_Ar), 192.67 (C=O).

24

To a magnetically stirred solution of dialkyl acetylene-dicarboxylate (2 mmol) and 2-hydroxy-1-aryl-2-(aryl-amino)ethanone (2 mmol) in CH₂Cl₂ (10 mL) was added a solution of alkyl isocyanide (2 mmol) in CH₂Cl₂ (5 mL) dropwise at r.t. over 10 min. The mixture was then allowed to stir for 24 h. The solvent was removed under reduced pressure, and the residue was separated by column chromatography (silica gel; hexane-EtOAc, 5:1) to afford the pure title compounds. 4a: yellow crystals (yield: 0.35 g, 89%); mp 172-173 ˚C. IR (KBr): 3385 (NH), 1729, 1677 (C=O) cm^-¹. MS (%): m/z = 402 (7) [M⁺]. Anal. Calcd for C₂₀H₂₂N₂O₇ ₍402): C, 59.70; H, 5.51; N, 6.96. Found: C, 59.82; H, 5.60; N, 6.82. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.25-2.06 (m, 10 H, 5 × CH₂ of Cy), 3.74 (m, 1 H, CHN), 3.78 (s, 3 H, OMe), 3.94 (s, 3 H, OMe), 6.73 (d, ^³ J _HH = 7.9 Hz, 1 H, NH), 7.61 (d, ^³ J _HH = 9.0 Hz, 2 H, 2 × CH of Ar), 8.21 (d, ^³ J _HH = 9.0 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 24.91, 25.77, 33.80 (5 × CH₂ of Cy), 52.13 (CHN), 51.80 (OMe), 53.41 (OMe), 89.23, 118.26, 124.40, 124.71, 135.41, 138.35, 146.39, 162.01 (C_Ar), 164.85 (CO₂Me), 165.81 (CO₂Me). 4b: yellow crystals (yield: 0.33 g, 90%); mp 173-174 ˚C. IR (KBr): 3420 (NH), 1730, 1675 (C=O) cm^-¹. MS (%): m/z = 376 (5) [M⁺]. Anal. Calcd for C₁₈H₂₀N₂O_7
(376): C, 57.44; H, 5.36; N, 7.44. Found: C, 57.55; H, 5.29; N, 7.49. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.51 (s, 9 H, CMe₃), 3.78 (s, 3 H, OMe), 3.96 (s, 3 H, OMe), 6.96 (s, 1 H, NH), 7.61 (d, ^³ J _HH = 8.8 Hz, 2 H,
2 × CH of Ar), 8.22 (d, ^³ J _HH = 8.8 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 29.75 (CMe ₃), 51.43 (CMe₃), 53.05 (OMe), 53.10 (OMe), 89.56, 117.46, 123.87, 124.38, 134.93, 138.26, 145.89, 161.87 (C_Ar), 164.53 (CO₂Me), 165.50 (CO₂Me). 4c: yellow oil (yield: 0.31 g, 91%). IR (KBr): 3345 (NH), 1732, 1672 (C=O) cm^-¹. MS (%): m/z = 385 (2) [M⁺]. Anal. Calcd for C₂₂H₂₇NO₅ ₍385): C, 68.55; H, 7.06; N, 3.63. Found: C, 68.63; H, 7.12; N, 3.60. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.27-2.12 (m, 10 H, 5 × CH₂ of Cy), 1.23 (t, ^³ J _HH = 7.1 Hz, 3 H, OCH₂CH ₃), 1.32 (t, ^³ J _HH = 7.1 Hz, 3 H, OCH₂CH ₃), 3.74 (m, 1 H, CHN), 4.13 (q, ^³ J _HH = 7.1 Hz, 2 H, OCH ₂CH₃), 4.26 (q, ^³ J _HH = 7.1 Hz, 2 H, OCH ₂CH₃), 6.73 (d, ^³ J _HH = 7.9 Hz, 1 H, NH), 7.39-7.58 (5 H, m, Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 14.47, 14.81 (2 × OCH₂ CH₃), 24.90, 25.78, 33.82 (5 × CH₂ of Cy), 52.07 (CHN), 60.42, 60.55 (2 × OCH₂CH₃), 89.43, 118.26, 124.40, 124.71, 135.41, 138.35, 146.39, 162.41 (C_Ar), 164.75 (CO₂Et), 165.81 (CO₂Et). 4d: yellow crystals (yield: 0.32 g, 89%); mp 95-97 ˚C. IR (KBr): 3335 (NH), 1735, 1679 (C=O) cm^-¹. MS (%): m/z = 365 (5) [M⁺]. Anal. Calcd for C₁₈H₂₀ClNO₅ ₍365): C, 59.10; H, 5.51; N, 3.83. Found: C, 59.22; H, 5.41; N, 3.72. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.45 (s, 9 H, CMe₃), 3.73 (s, 3 H, OMe), 3.87 (s, 3 H, OMe), 6.81 (s, 1 H, NH), 7.37 (d, ^³ J _HH = 8.6 Hz, 2 H, 2 × CH of Ar), 7.46 (d, ^³ J _HH = 8.6 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 30.12 (CMe ₃), 51.63 (CMe₃), 53.12 (OMe), 53.25 (OMe), 89.03, 114.27, 121.85, 126.39, 128.59, 132.33, 140.70, 162.00 (C_Ar), 165.30 (CO₂Me), 166.26 (CO₂Me). 4e: yellow crystals (yield: 0.39 g, 91%); mp 101-103 ˚C. IR (KBr): 3410 (NH), 1722, 1675 (C=O) cm^-¹. MS (%): m/z = 430 (7) [M⁺]. Anal. Calcd for C₂₂H₂₆N₂O₇ ₍385): C, 61.39; H, 6.09; N, 6.51. Found: C, 61.46; H, 6.14; N, 6.43. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.36-2.05 (m, 10 H, 5 × CH₂ of Cy), 1.30 (t, ^³ J _HH = 7.1 Hz, 3 H, OCH₂CH ₃), 1.39 (t, ^³ J _HH = 7.1 Hz, 3 H, OCH₂CH ₃), 3.72 (m, 1 H, CHN), 4.24 (q, ^³ J _HH = 7.2 Hz, 2 H, OCH ₂CH₃), 4.42 (q, ^³ J _HH = 7.2 Hz, 2 H, OCH ₂CH₃), 6.76 (d, ^³ J _HH = 7.9 Hz, 1 H, NH), 7.60 (d, ^³ J _HH = 8.9 Hz, 2 H, 2 × CH of Ar), 8.20 (d, ^³ J _HH = 8.9 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 14.42, 14.82 (2 × OCH₂ CH₃), 24.87, 25.78, 33.80 (5 × CH₂ of Cy), 52.06 (CHN), 60.42, 62.55 (2 × OCH₂CH₃), 89.52, 118.26, 124.71, 124.22, 135.55, 138.35, 146.39, 162.06 (C_Ar), 164.58 (CO₂Et), 165.38 (CO₂Et). 4f: yellow crystals (yield: 0.35 g, 88%); mp 99-101 ˚C. IR (KBr): 3335 (NH), 1735, 1679 (C=O) cm^-¹. MS (%): m/z = 409 (5) [M⁺]. Anal. Calcd for C₁₈H₂₀BrNO₅(409): C, 52.70; H, 4.91; N, 3.41. Found: C, 52.62; H, 4.80; N, 3.62. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.46 (s, 9 H, CMe₃), 3.75 (s, 3 H, OMe), 3.88 (s, 3 H, OMe), 6.81 (s, 1 H, NH), 7.32 (d, ^³ J _HH = 8.6 Hz, 2 H, 2 × CH of Ar), 7.44 (d, ^³ J _HH = 8.6 Hz, 2 H, 2 × CH of Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 30.34 (CMe ₃), 51.66 (CMe₃), 53.15 (OMe), 53.29 (OMe), 87.04, 112.18, 124.23, 126.22, 127.44, 131.79, 138.78, 162.05 (C_Ar), 163.38 (CO₂Me), 164.32 (CO₂Me). 4g: yellow crystals (yield: 0.28 g, 85%); mp 78-80 ˚C. IR (KBr): 3345 (NH), 1740, 1679 (C=O) cm^-¹. MS (%): m/z = 332 (5) [M⁺ + 1]. Anal. Calcd for C₁₈H₂₁NO₅ ₍331): C, 65.24; H, 6.39; N, 4.23. Found: C, 65.44; H, 6.35; N, 4.36. ^¹H NMR (500.1 MHz, CDCl₃): δ = 1.48 (s, 9 H, CMe₃), 3.77 (s, 3 H, OMe), 3.91 (s, 3 H, OMe), 6.82 (s, 1 H, NH), 7.24-7.66 (m, 5 H, Ar). ^¹³C NMR (125.7 MHz, CDCl₃): δ = 30.14 (CMe ₃), 51.46 (CMe₃), 52.95 (OMe), 53.69 (OMe), 88.52, 113.18, 124.23, 126.22, 127.44, 129.79, 140.23, 162.05 (C_Ar), 163.30 (CO₂Me), 166.12 (CO₂Me).