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

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

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;

Further Information

Publication History

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

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

1 Dean FA. Naturally Occurring Oxygen Ring Compounds Butterworth; London: 1963.

Google Scholar
2 Lipshutz BH. Chem. Rev. 1986, 86: 795

Crossref Google Scholar
3 Ugi I. Werner B. Dömling A. Molecules 2003, 8: 53

Crossref Google Scholar
4 Dömling A. Ugi I. Angew. Chem. Int. Ed. 2000, 39: 3168

Crossref PubMed Google Scholar
5 Nair V. Menon RS. Sreekumar V. Pure Appl. Chem. 2005, 77: 1191

Crossref Google Scholar
6 Dömling A. Chem. Rev. 2006, 106: 17

Crossref PubMed Google Scholar
7 Nair V. Unni Vinod A. Abhilash N. Rajeev Menon S. Santhi V. Luxmi Varma R. Viji S. Mathew S. Srinivas R. Tetrahedron 2003, 59: 10279

Crossref Google Scholar
8 Yadav JS. Subba Reddy BV. Shubashree S. Sadashiv K. Krishna Rao D. J. Mol. Catal. A.: Chem. 2007, 272: 128

Crossref Google Scholar
9 Nair V. Menon RS. Deepthi A. Devi BR. Biju AT. Tetrahedron Lett. 2005, 46: 1337

Crossref Google Scholar
10 Nair V. Deepthi A. Tetrahedron Lett. 2006, 47: 2037

Crossref Google Scholar
11 Nair V. Vinod AU. J. Org. Chem. 2001, 66: 4427

Crossref Google Scholar
12 Alizadeh A. Rostamnia S. Zohreh N. Bijanzadeh HR. Chem. Month. 2008, 139: 49

Crossref Google Scholar
13 Anary-Abbasinejad M. Mosslemin MH. Anaraki-Ardakani H. Tahan S. J. Chem. Res. 2006, 306

Crossref Google Scholar
14 Anary-Abbasinejad M. Mosslemin MH. Tahan S. Anaraki-Ardakani H. J. Chem. Res. 2006, 170

Crossref Google Scholar
15 Anary-Abbasinejad M. Anaraki-Ardakani H. Rastegari F. Hassanabadi A. J. Chem. Res. 2007, 602

Crossref Google Scholar
16 Yavari I. Djahaniani H. Nasiri F. Tetrahedron 2003, 59: 9409

Crossref Google Scholar
17 Shaabani A. Teimouri MB. Bijanzadeh HR. J. Chem. Res. 2002, 381

Crossref Google Scholar
18 Shaabani A. Teimouri MB. Mirzaei P. Bijanzadeh HR. J. Chem. Res. 2003, 82

Crossref Google Scholar
19 Alizadeh A. Rostamnia S. Zhu LZ. Synthesis 2008, 1788

Article in Thieme Connect Google Scholar
20 Anary-Abbasinejad M. Ghanea F. Anaraki-Ardakani H. Synth. Commun. 2009, 39: 544

Crossref Google Scholar
21 Anary-Abbasinejad M. Anaraki-Ardakani H. Ghanea F. Monatsh. Chem. 2009, 140: 397

Crossref Google Scholar
22 Anary-Abbasinejad M. Moslemine MH. Anaraki-Ardakani H. J. Fluorine Chem. 2009, 130: 368

Crossref Google Scholar

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).