The First Facile Synthesis of Some 1,2a,3,8b-Tetrahydro-2H-Cyclobuta[c] Chromenes Through Intramolecular Alkylation of an Aromatic Ring by a Cyclobutanone

Angela M. Bernard; Costantino Floris; Angelo Frongia; Pier P. Piras

doi:10.1055/s-2002-25355

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Synlett 2002(5): 0796-0798
DOI: 10.1055/s-2002-25355

LETTER

The First Facile Synthesis of Some 1,2a,3,8b-Tetrahydro-2H-Cyclobuta[c] Chromenes Through Intramolecular Alkylation of an Aromatic Ring by a Cyclobutanone

Angela M. Bernard, Costantino Floris, Angelo Frongia, Pier P. Piras*
Dipartimento di Scienze Chimiche, Università di Cagliari, Complesso Universitario di Monserrato, S.S. 554, Bivio per Sestu, I-09042 Monserrato (Cagliari), Italy
Fax: +39(70)6754388; e-Mail: pppiras@unica.it;

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Publication History

Received 7 February 2002
Publication Date:
07 February 2007 (online)

Abstract
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Abstract

Starting from cyclobutanones several new chromenes containing a cyclobutane ring are prepared. Ring fission of these derivatives gives easy access to functionalized 3-isoflavenes.

Key words

cyclopropanes - cyclobutanones - electrophilic aromatic substitutions - ring opening - kinetic resolution

References

1 For a review see: Bellus D. Ernst B. Angew. Chem. Int. Ed. Engl. 1988, 27: 797

Crossref Google Scholar
2a Nemoto H. Ishibashi H. Nagamochi M. Fukumoto K. J. Org. Chem. 1992, 57: 1707

Google Scholar
2b Nemoto H. Shiraki M. Fukumoto K. Tetrahedron 1994, 50: 10391

Google Scholar
2c Nemoto H. Miyata J. Fukumoto K. Heterocycles 1996, 42: 165

Google Scholar
2d Nemoto H. Miyata J. Yoshida M. Raku N. Fukumoto K. J. Org. Chem. 1997, 62: 7850

Google Scholar
2e Chevtchouk T. Ollivier J. Salaun J. Tetrahedron: Asymmetry 1997, 8: 1011

Google Scholar
2f Cho SY. Cha JK. Org. Lett. 2000, 9: 1337

Google Scholar
3a Trost BM. Top. Curr. Chem. 1986, 133: 3

Google Scholar
3b Salaun J. Top. Curr. Chem. 1988, 144: 1

Google Scholar
4 For a review see: Conia JM. Salaun J. Acc. Chem. Res. 1972, 5: 33

Crossref Google Scholar
5a Salaun JR. Conia JM. J. Chem. Soc., Chem. Commun. 1971, 1580

Google Scholar
5b Salaun J. Garnier B. Conia JM. Tetrahedron 1974, 30: 1413

Google Scholar
5c Salaun J. Champion J. Conia JM. Org. Synth. 1977, 57: 46

Google Scholar
5d Salaun J. Champion J. Conia JM. Org. Synth. Coll. Vol. VI 1988, 320

Google Scholar
Some derivatives have been previously reported. For 1a-e, g see:
7a Bernard AM. Piras PP. Synth. Commun. 1997, 27: 709

Crossref Google Scholar
7b Bernard AM. Piras PP. Synlett 1997, 5: 585

Crossref Google Scholar
7c Brandi A. Carli S. Goti A. Heterocycles 1988, 27: 17

Crossref Google Scholar
7d For 2a,b, 3a see: Bernard AM. Floris C. Frongia A. Piras PP. Synlett 1998, 668

Crossref Google Scholar
7e For 3b see: Bernard AM. Floris C. Frongia A. Piras PP. Tetrahedron 2000, 56: 4555

Crossref Google Scholar
9a Gauthier S. Caron B. Cloutier J. Dory YL. Favre A. Larouche D. Mailhot J. Ouellet C. Schwerdtfeger A. Leblanc G. Martel C. Simard J. Merand Y. Belanger A. Labrie C. Labrie F. J. Med. Chem. 1997, 40: 2117

Crossref Google Scholar
9b Varma RS. Dahiya R. J. Org. Chem. 1998, 63: 8038

Crossref Google Scholar

6

It has not been possible to isolate the oxaspiropentane 2e, as it is transformed to the corresponding cyclobutanone 3e during the epoxidation reaction.

8

Typical procedure for the preparation of chromenes 4a-f: A stirred solution of cyclobutanone 3 (2.7 mmol) and p-toluenesulfonic acid (0.27 mmol, 0.046 g) in benzene (10 mL) was refluxed for 6 h. The reaction mixture was diluted with CH₂Cl₂ and washed with 10% NaHCO₃ and brine, dried (Na₂SO₄) and evaporated to remove the solvent. The residue was purified by chromatography on silica gel with Et₂O-light petroleum (1:1) as eluent.
All new compounds have been fully characterized by ¹H NMR (300 MHz), ¹³C NMR (75.4 MHz) and mass spectra (70 eV). Analytical data for some representative derivatives are reported. 1f: colorless oil; yield: 70%. ¹H NMR (CDCl₃) δ: 1.00-1.22 (m. 4 H), 1.52 (d, 3 H, J = 6.6 Hz), 1.84 (s, 3 H), 5.05 (q, 1 H, J = 6.6 Hz), 6.90-7.28 (m, 5 H). ¹³C NMR (CDCl₃) δ: 1.14, 2.76, 15.10, 19.71, 78.56, 115.65, 118.76, 120.65, 124.74, 129.12, 158.16. 3e: yellow oil; yield: 85%. ¹H NMR (CDCl₃) δ: 2.48-2.58 (m, 1 H), 2.73-2.82 (m, 1 H), 2.98-3.10 (m, 1 H), 3.18-3.30 (m, 1 H), 3.97, 4.23 (AB q, 2 H, J = 9 Hz), 7.22-7.44 (m, 10 H). ¹³C NMR (CDCl₃) δ: 21.09, 44.09, 72.06, 72.54, 114.58, 121.25, 126.58, 127.50, 128.69, 129.43, 137.83, 158.43, 210.17. IR (neat, cm^-1) : 1782. MS m/z: 252 [M⁺ (0.4)], 209(5), 195(9), 159(100), 131(23), 117(60). 4e: yellow oil; yield 60%. ¹H NMR (CDCl₃) δ: 2.13-2.27 (m, 1 H), 2.19 (br s, 1 H), 2.26-2.33 (m, 2 H), 2.54-2.61 (m, 1 H), 4.05,4.14 (AB q, 2 H, J = 11.4 Hz), 6.85-7.65 (m, 9 H). ¹³C NMR (CDCl₃) δ: 19.94, 36.76, 52.91, 71.74, 72.68, 117.29, 122.08, 127.22, 127.32, 127.58, 128.57, 128.79, 129.73, 138.37, 154.17. IR (neat, cm^-1) : 3450. MS m/z: 252 [M⁺(6)], 234(5), 224(8), 121(100). 5e: red oil; yield 56%. ¹H NMR (CDCl₃) δ: 2.41 (s, 3 H), 2.81 (t, 2 H, J = 7.5 Hz), 3.99 (t, 2 H, J = 7.5 Hz), 4.78 (s, 2 H), 6.81-7.64 (m, 10 H). ¹³C NMR (CDCl₃) δ: 21.55, 26.98, 68.19, 69.39, 116.19, 121.51, 122.60, 123.25, 124.00, 127.69, 127.78, 128.02, 128.77, 128.91, 129.69, 132.69, 134.34, 13.44, 144.54, 153.89. IR (neat, cm^-1): 1160,1350.