Synlett 2012; 23(10): 1481-1484
DOI: 10.1055/s-0031-1291012
letter
© Georg Thieme Verlag Stuttgart · New York

Electrophilic Iodo-Mediated Cyclization in PEG under Microwave Irradiation: Easy Access to Highly Functionalized Furans and Pyrroles

Rosella Spina
a   Institut des Biomolécules Max Mousseron (IBMM) UMR 5247 CNRS, UM I-UM II Université de Montpellier II, Place E. Bataillon, 34095 Montpellier Cedex 5, France, Fax: +33(467)144866   eMail: frederic.lamaty@univ-montp2.fr
b   Dipartimento di Scienze Farmaceutiche, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy
,
Evelina Colacino
a   Institut des Biomolécules Max Mousseron (IBMM) UMR 5247 CNRS, UM I-UM II Université de Montpellier II, Place E. Bataillon, 34095 Montpellier Cedex 5, France, Fax: +33(467)144866   eMail: frederic.lamaty@univ-montp2.fr
,
Bartolo Gabriele
b   Dipartimento di Scienze Farmaceutiche, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy
,
Giuseppe Salerno
c   Dipartimento di Chimica, Università della Calabria, 87036 Arcavacata di Rende (CS), Italy
,
Jean Martinez
a   Institut des Biomolécules Max Mousseron (IBMM) UMR 5247 CNRS, UM I-UM II Université de Montpellier II, Place E. Bataillon, 34095 Montpellier Cedex 5, France, Fax: +33(467)144866   eMail: frederic.lamaty@univ-montp2.fr
,
Frédéric Lamaty*
a   Institut des Biomolécules Max Mousseron (IBMM) UMR 5247 CNRS, UM I-UM II Université de Montpellier II, Place E. Bataillon, 34095 Montpellier Cedex 5, France, Fax: +33(467)144866   eMail: frederic.lamaty@univ-montp2.fr
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Publikationsverlauf

Received: 17. Februar 2012

Accepted after revision: 23. März 2012

Publikationsdatum:
25. Mai 2012 (online)


Abstract

The rapid and facile synthesis of highly substituted β-iodofurans and β-iodopyrroles is reported using a mixture of molecular iodine and a base in solid PEG 3400 as alternative, eco-friendly and nontoxic solvent under microwave irradiation, in a very short time. The heterocycles are efficiently recovered in good yields by a simple workup procedure, avoiding chromatographic purification.

 
  • References

  • 1 Pradal A, Nasr A, Toullec PY, Michelet V. Org. Lett. 2010; 12: 5222
  • 2 Lee Y, Lim C, Kim S, Shin S. Bull. Korean Chem. Soc. 2010; 31: 670
  • 3 Mehta S, Larock RC. J. Org. Chem. 2010; 75: 1652
  • 4 Yao T, Yue D, Larock RC. J. Org. Chem. 2005; 70: 9985
  • 5 Cho C.-H, Larock RC. Tetrahedron Lett. 2010; 51: 3417
  • 6 Kaur P, Singh P, Kumar S. Tetrahedron 2005; 61: 8231
  • 7 Arcadi A, Cacchi S, Fabrizi G, Marinelli F, Moro L. Synlett 1999; 1432
  • 8 Chen Z, Huang G, Jiang H, Huang H, Pan X. J. Org. Chem. 2011; 76: 1134
  • 9 Crone B, Kirsch SF. J. Org. Chem. 2007; 72: 5435
  • 10 Bew SP, El-Taeb GM. M, Jones S, Knight DW, Tan W.-F. Eur. J. Org. Chem. 2007; 5759
  • 11 Badry MG. A, Kariuki B, Knight DW. M. F. K. Tetrahedron Lett. 2009; 50: 1385
  • 12 Mancuso R, Mehta S, Gabriele B, Salerno G, Jenks WS, Larock RC. J. Org. Chem. 2010; 75: 897
  • 13 Yue D, Ca ND, Larock RC. J. Org. Chem. 2006; 71: 3381
  • 14 Amjad M, Knight DW. Tetrahedron Lett. 2006; 47: 2825
  • 15 Yoshida M, Easmin S, Al-Amin M, Hirai Y, Shishido K. Tetrahedron 2011; 67: 3194
  • 16 Knight DW, Rost HC, Sharland CM, Singkhonrat J. Tetrahedron Lett. 2007; 48: 7906
  • 17 Okitsu T, Sato K, Potewar TM, Wada A. J. Org. Chem. 2011; 76: 3438
  • 18 Kim K, Kim I. J. Comb. Chem. 2010; 12: 379
  • 19 Cho C.-H, Neuenswander B, Larock RC. J. Comb. Chem. 2010; 12: 278
  • 20 Togo H, Iida S. Synlett 2006; 2159
  • 21 Declerck V, Martinez J, Lamaty F. Synlett 2006; 3029
  • 22 Colacino E, Villebrun L, Martinez J, Lamaty F. Tetrahedron 2010; 66: 3730
  • 23 Declerck V, Ribiere P, Nedellec Y, Allouchi H, Martinez J, Lamaty F. Eur. J. Org. Chem. 2007; 201
  • 24 Sauvagnat B, Lazaro R, Martinez J, Lamaty F. Tetrahedron Lett. 2000; 41: 6371
  • 25 Colacino E, Daich L, Martinez J, Lamaty F. Synlett 2007; 1279
  • 26 Typical Experimental Procedure: A mixture of I2 (25 mg, 0.1 mmol), NaHCO3 (0.1 mmol), PEG 3400 (350 mg) and substrate 1a (0.05 mmol) was reacted under microwave irradiation at 50 °C (initial power 400 W) for 10 min. The reaction mixture was diluted with CH2Cl2 (2.0 mL), precipitated in Et2O (250 mL), cooled for 3 h at –18 °C to improve PEG precipitation and filtered. The organic phase was washed with a saturated solution of sodium thiosulfate (Na2S2O3) to neutralize the excess of iodine. Compound 2a was recovered as a yellow oil in 81% yield. Spectral data for 2a: 1H NMR (300 MHz, CDCl3): δ = 7.55–7.58 (m, 2 H), 7.31–7.43 (m, 8 H), 3.00 (d, J = 7.1 Hz, 2 H), 2.03 (m, 1 H), 1.18 (s, 9 H), 1.04 (d, J = 6.6 Hz, 3 H), 1.02 (d, J = 6.6 Hz, 3 H). 13C NMR (300 MHz, CDCl3): δ = 148.6, 140.3, 134.8, 134.3, 128.26, 127.8, 123.8, 112.7, 93.6, 84.5, 84.4, 75.1, 36.3, 29.7, 27.0, 22.6. HMRS (ESI): m/z [M + H]+ calcd for C27H29NO2I: 526.1243; found: 526.1245
  • 27 Langle S, Ngi SI, Anselmi E, Abarbri M, Thibonnet J, Duchêne A. Synthesis 2007; 1724
  • 28 Ji K.-G, Zhu H.-T, Yang F, Shaukat A, Xia X.-F, Yang Y.-F, Liu X.-Y, Liang Y.-M. J. Org. Chem. 2010; 75: 5670
  • 29 Ke-Gong J, Hai-Tao Z, Fang Y, Xing-Zhong S, Shu-Chun Z, Xue-Yuan L, Ali S, Yong-Min L. Chem.–Eur. J. 2010; 16: 6151
  • 30 Spectral data for 2g: 1H NMR (400 MHz, CDCl3): δ = 0.93 (t, J = 7.2 Hz, 3 H), 0.94 (t, J = 7.2 Hz, 3 H), 1.33 (s, 9 H), 1.38–1.61 (m, 8 H), 2.43 (t, J = 7.2 Hz, 2 H), 2.87 (dd, 2 H), 4.37 (s, 2 H), 7.07–7.14 (m, 2 H), 7.16–7.25 (m, 3 H). 13C NMR (300 MHz, CDCl3): δ = 148.6, 139.8, 136.3, 136.0, 128.2, 128.0, 125.9, 113.6, 94.5, 84.6, 74.6, 74.5, 33.7, 31.2, 31.0, 29.3, 27.4, 22.5, 22.0, 19.3, 14.0, 13.6. ESI–MS (+): m/z = 520.1 [M +H]+, 464.0 [M + H – t-Bu]+, 419.9 [M + 2 H – Boc]+. Spectral data for 3g: 1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.2 Hz, 3 H), 0.98 (t, J = 7.3 Hz, 3 H), 1.26 (s, 9 H), 1.40–1.51 (m, 8 H), 2.69–2.76 (m, 1 H), 2.82–2.92 (m, 3 H), 4.14 (s, 2 H), 7.10–7.17 (m, 3 H), 7.22–7.26 (m, 2 H). 13C NMR (300 MHz, CDCl3): δ = 148.7, 138.7, 136.8, 134.1, 129.4, 128.3, 128.2, 125.9, 111.1, 89.5, 84.7, 71.3, 49.7, 33.5, 32.0, 30.6, 29.1, 27.2, 22.5, 21.7, 14.1