Furo[3,4-b]chromones, and not Pyrano[3,4-b]chromones, are Obtained by the Reaction of 3-Formylchromones with Isocyanides

Ana G. Neo; Leda Garrido; Jesús Díaz; Stefano Marcaccini; Carlos F. Marcos

doi:10.1055/s-0032-1317032

Synlett, Table of Contents

Synlett 2012; 23(15): 2227-2230
DOI: 10.1055/s-0032-1317032

letter

Furo[3,4-b]chromones, and not Pyrano[3,4-b]chromones, are Obtained by the Reaction of 3-Formylchromones with Isocyanides

Ana G. Neo

^aLaboratorio de Química Orgánica y Bioorgánica (L.O.B.O.), Departamento de Química Orgánica e Inorgánica, Facultad de Veterinaria, Universidad de Extremadura, 10071 Cáceres, Spain, Fax: +34(927)257110 Email: cfernan@unex.es

,

Leda Garrido

^aLaboratorio de Química Orgánica y Bioorgánica (L.O.B.O.), Departamento de Química Orgánica e Inorgánica, Facultad de Veterinaria, Universidad de Extremadura, 10071 Cáceres, Spain, Fax: +34(927)257110 Email: cfernan@unex.es

,

Jesús Díaz

^aLaboratorio de Química Orgánica y Bioorgánica (L.O.B.O.), Departamento de Química Orgánica e Inorgánica, Facultad de Veterinaria, Universidad de Extremadura, 10071 Cáceres, Spain, Fax: +34(927)257110 Email: cfernan@unex.es

,

Stefano Marcaccini

^bDipartimento di Chimica ‘Ugo Schiff’, Università di Firenze, 50019 Sesto Fiorentino FI, Italy

,

Carlos F. Marcos*

^aLaboratorio de Química Orgánica y Bioorgánica (L.O.B.O.), Departamento de Química Orgánica e Inorgánica, Facultad de Veterinaria, Universidad de Extremadura, 10071 Cáceres, Spain, Fax: +34(927)257110 Email: cfernan@unex.es

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Abstract

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Abstract

The reaction of formylchromones with alkyl isocyanides was reinvestigated. In earlier reports from other research groups, two different structures were proposed for the products of this reaction. Herein, we provide unambiguous evidence that these products are chromenylmethylene furochromenones and not pyranochromones. Our structure assignment is based on X-ray diffraction analysis and two-dimensional NMR methods. The knowledge of the correct structure of these compounds is essential for the design of derivatives with potential applications as bioactive molecules or fluorescent biomarkers.

Key words

cycloaddition reactions - furans - fused-ring systems - multicomponent reactions - heterocycles - natural products

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References

References and Notes

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16 General procedure for the cycloaddition of formyl-chromones and isocyanides: Isocyanide 2 (2.5 mmol) was added to a solution of formyl chromone 1 (5 mmol) in anhydrous THF (5 mL). The resulting solution was heated at reflux under N₂ for 5–8 h, and cooled to 0 °C. The precipitate was collected by filtration. An additional amount of product was recovered by concentration of the filtrate and purification by column chromatography
17 Representative data: 7-Methyl-1-[1-(6-methyl-4-oxo-4H-1-benzopyran-3-yl)-meth-(Z)-ylidene]-3-[(Z)-pentylimino]-1,3-dihydrofuro[3,4-b][1]benzopyran-9-one (3f): Yield: 61%; yellow solid; mp 230–231 °C; IR: 1676, 1651, 1618, 1484, 816 cm^–1; ¹H NMR (400 MHz, CDCl₃): δ = 8.69 (br s, 1 H, CH-2′), 8.09 (br s, 1 H, CH-8), 8.05 (br s, 1 H, CH-5′), 7.56 (d, J = 8.5 Hz, 1 H, CH-5), 7.53 (dd, J = 8.5, 2.1 Hz, 1 H, CH-6), 7.42 (dd, J = 8.5, 2.1 Hz, 1 H, CH-7′), 7.34 (d, J = 8.5 Hz, 1 H, CH-8′), 7.13 (br s, 1 H, CH-9′), 3.72 [t, J = 7.0 Hz, 2 H, CH ₂(CH₂)₃CH₃], 2.48 (s, 3 H, C7-CH ₃), 2.44 (s, 3 H, C6′-CH ₃), 1.82 [m, 2 H, CH₂CH ₂(CH₂)₂CH₃], 1.47 [m, 2 H, -(CH₂)₂CH ₂CH₂CH₃], 1.43 [m, 2 H, -(CH₂)₃CH ₂CH₃], 0.95 [t, J = 7.2 Hz, 3 H, -(CH₂)₄CH ₃]; ¹³C NMR (100 MHz, CDCl₃): δ = 174.9 [C(4′)=O], 172.3 [C(9)=O], 155.8 (CH-2′), 154.5 (C-4a), 154.0 (C-8a′), 152.6 (C-3a), 148.2 (C-3), 143.9 (C-1), 136.3 (C-7), 135.8 (CH-6), 135.3 (C-6′), 134.8 (CH-7′), 125.8 (CH-8), 125.7 (CH-5′), 124.3 (C-8a), 123.2 (C-4a′), 119.9 (C-9a), 119.2 (C-3′), 118.6 (CH-5), 117.8 (CH-8′), 97.1 (CH-9′), 49.1 [-CH ₂-(CH₂)₃CH₃], 30.2 [-CH₂CH ₂(CH₂)₂CH₃], 29.7 [-(CH₂)₂CH ₂CH₂CH₃], 22.5 [-(CH₂)₃CH ₂CH₃], 20.9 (2 × ArCH₃), 14.0 [-(CH₂)₄CH ₃]; MS (EI): m/z (%) = 455 (73) [M⁺], 412 (56), 398 (60), 384 (54), 371 (100), 222 (23), 134 (41); HRMS (EI): m/z calcd for C₂₈H₂₅NO₅: 455.1733; found: 455.1741
18 CCDC 886508 contains the supplementary crystallographic data for compound 3a can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
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