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Synlett 2012; 23(10): 1481-1484
DOI: 10.1055/s-0031-1291012
DOI: 10.1055/s-0031-1291012
letter
Electrophilic Iodo-Mediated Cyclization in PEG under Microwave Irradiation: Easy Access to Highly Functionalized Furans and Pyrroles
Weitere Informationen
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.
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- 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
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- 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