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DOI: 10.1055/s-2004-837220
Short and Efficient Synthesis of Cadiolide B
Publikationsverlauf
Publikationsdatum:
22. Dezember 2004 (online)
Abstract
The first synthesis of cadiolide B has been achieved in 6 steps and 42% overall yield from 4-bromo-2(5H)-furanone. The pathway involves sequential, regiocontrolled introduction of the three furanone substituents by means of aldol reactions and Suzuki cross coupling.
Key words
cross coupling - aldol reaction - 2-furanolates - lactones - total synthesis
- 1
Smith CJ.Hettich RL.Jompa J.Tahir A.Buchanan MV.Ireland CM. J. Org. Chem. 1998, 63: 4147 - 2
Miao S.Andersen RJ. J. Org. Chem. 1991, 56: 6275 - 3
Boukouvalas J.Lachance N.Ouellet M.Trudeau M. Tetrahedron Lett. 1998, 39: 7665 - 4a
Carroll AR.Healy PC.Quinn RJ.Tranter CJ. J. Org. Chem. 1999, 64: 2680 - 4b
Ortega MJ.Zubía E.Ocaña JM.Naranjo S.Salvá J. Tetrahedron 2000, 56: 3963 - 5
Prasit P.Wang Z.Brideau C.Chan C.-C.Charleson S.Cromlish W.Ethier D.Evans JF.Ford-Hutchinson AW.Gauthier JY.Gordon R.Guay J.Gresser M.Kargman S.Kennedy B.Leblanc Y.Léger S.Mancini J.O’Neill GP.Ouellet M.Percival MD.Perrier H.Riendeau D.Rodger I.Tagari P.Thérien M.Vickers P.Wong E.Xu L.-J.Young RN.Zamboni R.Boyce S.Rupniak N.Forrest M.Visco D.Patrick D. Bioorg. Med. Chem. Lett. 1999, 9: 1773 - 6
Jas G. Synthesis 1991, 965 - 7
Jefford CW.Jaggi D.Boukouvalas J. J. Chem. Soc., Chem. Commun. 1988, 1595 - 9
Ruel FS.Braun MP.Johnson CR. Org. Synth., Collect. Vol. 75 1998, 69 - 10 See also:
Uenishi J.Beau J.-M.Armstrong RW.Kishi Y. J. Am. Chem. Soc. 1987, 109: 4756MissingFormLabel - 14
Kotora M.Negishi E. Synthesis 1997, 121
References
Compound 6: yellow oil. 1H NMR (300 MHz, CDCl3): δ = 3.66 (br s, 1 H), 3.79 (s, 3 H), 4.82 (s, 2 H), 5.62 (s, 1 H), 6.89 (d, J = 8.7 Hz, 2 H), 7.38 (d, J = 8.7 Hz, 2 H). 13C NMR (75 MHz, CDCl3): δ = 55.2, 69.0, 73.4, 114.1, 127.1, 132.1, 132.4, 139.3, 159.6, 170.2. Anal. Calcd for C12H11BrO4: C, 48.19; H, 3.71. Found: C, 48.13; H, 3.57.
11Compound 7: white solid; mp 90-92 °C. 1H NMR (300 MHz, CDCl3): δ = 3.78 (s, 3 H), 3.82 (s, 3 H), 4.15 (d, J = 9.8 Hz, 1 H), 5.03 (d, J = 16.9 Hz, 1 H), 5.22 (d, J = 16.9 Hz, 1 H), 5.79 (d, J = 9.8 Hz, 1 H), 6.88 (d, J = 8.6 Hz, 2 H), 6.93 (d, J = 8.8 Hz, 2 H), 7.29 (d, J = 8.8 Hz, 2 H), 7.38 (d, J = 8.6 Hz, 2 H). 13C NMR (75 MHz, CDCl3): d = 55.2, 55.3, 68.4, 70.8, 114.1, 114.6, 122.4, 124.8, 127.7, 129.2, 133.4, 156.8,
159.3, 161.6, 174.6. HRMS: m/z calcd for C19H18O5: 326.1154; found: 326.1158.
Compound 8: yellow solid; mp 166-167 °C. 1H NMR (300 MHz, CDCl3): d = 3.79 (s, 3 H), 3.85 (s, 3 H), 5.30 (s, 2 H), 6.84 (d, J = 8.8 Hz, 2 H), 6.92 (d, J = 8.8 Hz, 2 H), 7.36 (d, J = 8.8 Hz, 2 H), 7.91 (d, J = 8.8 Hz, 2 H). 13C NMR (75 MHz, CDCl3): d = 55.3, 55.5, 70.3, 114.1, 114.6, 121.4, 123.4, 128.7, 129.6, 132.0, 159.7, 162.4,
164.6, 171.1, 190.1. Anal. Calcd for C19H16BrO5: C, 70.36; H, 4.97. Found: C, 70.12; H, 5.02.
Compound 9: yellow solid; 189-190 °C. 1H NMR (300 MHz, CDCl3): δ = 3.79 (s, 3 H), 3.81 (s, 3 H), 3.84 (s, 3 H), 6.23 (s, 1 H), 6.84 (d, J = 8.6 Hz, 2 H), 6.87 (d, J = 8.6 Hz, 2 H), 6.92 (d, J = 8.6 Hz, 2 H), 7.36 (d, J = 8.6 Hz, 2 H), 7.80 (d, J = 8.6 Hz, 4 H). 13C NMR (75 MHz, CDCl3): δ = 55.2, 55.3, 55.4, 113.7, 114.2, 114.4, 116.8, 121.3, 122.7, 125.7, 129.2, 130.7, 132.0, 132.9, 145.7, 156.8, 160.9, 161.2, 164.1, 166.6, 188.1. HRMS: m/z calcd for C27H22O6: 442.1416; found: 442.1424.
13Compound 10: yellow solid; 262-263 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 6.33 (s, 1 H), 6.77 (d, J = 8.7 Hz, 2 H), 6.80 (d, J = 8.6 Hz, 2 H), 6.88 (d, J = 8.7 Hz, 2 H), 7.23 (d, J = 8.6 Hz, 2 H), 7.70 (d, J = 8.7 Hz, 2 H), 7.75 (d, J = 8.7 Hz, 2 H), 10.06 (br s, 1 H), 10.18 (br s, 1 H), 10.55 (br s, 1 H). 13C NMR (75 MHz, DMSO-d 6): δ = 115.5, 115.8, 116.1, 116.4, 119.5, 121.5, 124.1, 127.5, 130.9, 132.2, 133.1, 144.7, 156.0, 159.4, 159.6, 163.1, 166.1, 188.1. HRMS: m/z calcd for C24H16O6: 400.0947; found: 400.0956.