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Synlett 2008(17): 2583-2586  
DOI: 10.1055/s-0028-1083497
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of γ-Alkylidene α,β-Unsaturated δ-Lactones by Ring-Closing Metathesis: Application to the Synthesis of the C1-C8 Subunit of Biselide E

Anne-Frédérique Salit, Marion Barbazanges, Frédéric Miege, Marie-Hélène Larraufie, Christophe Meyer*, Janine Cossy*
Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS, 10 Rue Vauquelin, 75231 Paris Cedex 05, France
Fax: +33(1)40794660; e-Mail: christophe.meyer@espci.fr; e-Mail: janine.cossy@espci.fr;
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Publication History

Received 28 May 2008
Publication Date:
01 October 2008 (online)

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Abstract

The synthesis of γ-alkylidene α,β-unsaturated δ-lactones was achieved by ring-closing metathesis of acrylates derived from (1,3-butadien-2-yl)methanols. The application to the synthesis of the C1-C8 subunit of biselide E is reported.

Keywords

ring-closing metathesis - 1,3-dienes - lactones - cross-coupling reactions - biselide E

    References and Notes

  • 1 Thomas H. Budzikiewicz H. Phytochemistry  1980,  19:  1866 
    CrossrefGoogle Scholar
  • 2 Ichikawa K. Hirai H. Ishiguro M. Kambara T. Kato Y. Kim YJ. Kojima Y. Matsunaga Y. Nishida H. Shiomi Y. Yoshikawa N. Huang LH. Kojima N. J. Antibiot.  2001,  54:  697 
    Google Scholar
  • 3a Dorner JW. Cole RJ. Springer JP. Cox RH. Cutler H. Wicklow DT. Phytochemistry  1980,  19:  1157 
    Google Scholar
  • 3b Barrero AF. Herrador MM. Quílez del Moral JF. Valdivia MV. Org. Lett.  2002,  4:  1379 
    Google Scholar
  • 4a Silva M. Bittner M. Sammes PG. Phytochemistry  1973,  12:  883 
    Google Scholar
  • 4b Ying B.-P. Kubo I. . Matsumoto T. Hayashi Y. Phytochemistry  1990,  29:  3953 
    Google Scholar
  • 4c Kubo I. Himejima M. Ying B.-P. Phytochemistry  1991,  30:  1467 
    Google Scholar
  • 4d Pettit GR. Tan R. Herald DL. Hamblin J. Pettit RK. J. Nat. Prod.  2003,  66:  276 
    Google Scholar
  • 5 Lee H.-J. Lee C.-H. Chung M.-C. Chun H.-K. Rhee J.-S. Kho Y.-H. Tetrahedron Lett.  1999,  40:  6949 
    CrossrefGoogle Scholar
  • 6 Chiaroni A. Riche C. Khuong-Huu Q. Nguyen-Ngoc H. Nguyen-Viet K. Khuong-Huu F. Acta Crystallogr., Sect. C  2000,  56:  711 
    CrossrefGoogle Scholar
  • 7 Teruya T. Suenaga K. Maruyama S. Kurotaki M. Kigoshi H. Tetrahedron  2005,  61:  6561 
    CrossrefGoogle Scholar
  • 8 Choi T.-L. Grubbs RH. Chem. Commun.  2001,  2648 
    CrossrefGoogle Scholar
  • 9 Vedrenne E. Royer F. Oble J. El Kaïm L. Grimaud L. Synlett  2005,  2379 
    Article in Thieme ConnectGoogle Scholar
  • 10 Trnka TM. Day MW. Grubbs RH. Organometallics  2001,  20:  3845 
    CrossrefGoogle Scholar
  • 11 For a review, see: Diver ST. Giessert AJ. Chem. Rev.  2004,  104:  1317 
    Google Scholar
  • 13 For a review on macrocyclizations by RCM (including 1,3-dienes as olefinic partners), see: Gradillas A. Pérez-Castells J. Angew. Chem. Int. Ed.  2006,  45:  6086 
    Google Scholar
  • For cross-metathesis involving conjugated dienes, see:
  • 14a Funk TW. Efskind J. Grubbs RH. Org. Lett.  2005,  7:  187 
    Google Scholar
  • 14b Ferrié L. Amans D. Reymond S. Bellosta V. Capdevielle P. Cossy J. J. Organomet. Chem.  2006,  691:  5456 
    Google Scholar
  • 14c Moura-Letts G. Curran DP. Org. Lett.  2007,  9:  5 
    Google Scholar
  • 15 Some lactones of type B have been prepared by a Pd-catalyzed annulation of allenes with (Z)-3-iodoacrylic acid, see: Larock RC. He Y. Leong WW. Han X. Refvik MD. Zenner JM. J. Org. Chem.  1998,  63:  2154 ; unfortunately, the reaction proceeds with low regioselectivity for monosubstituted allenes
    CrossrefGoogle Scholar
  • 16 The α-bromoenals were prepared from the corresponding enals, see: Kowalski CJ. Weber AE. Fields KW. J. Org. Chem.  1982,  47:  5088 
    CrossrefGoogle Scholar
  • 17 Molander GA. Felix LA. J. Org. Chem.  2005,  70:  3950 
    CrossrefGoogle Scholar
  • These compounds were prepared by Pd-catalyzed hydrostannylation of the corresponding acetylenic esters followed by iododestannylation, see:
  • 18a Zhang HX. Guibé F. Balavoine G. J. Org. Chem.  1990,  55:  1857 
    Google Scholar
  • 18b Rossi R. Carpita A. Cossi P. Tetrahedron  1992,  48:  8801 
    Google Scholar
  • 20 Alonso DA. Najera C. Sansano JM. Tetrahedron  1994,  50:  6603 ; compound 12 is sensitive and can undergo polymerization upon concentration of its solutions
    CrossrefGoogle Scholar
  • 23 Tan Z. Negishi E. Angew. Chem. Int. Ed.  2006,  45:  762 
    CrossrefGoogle Scholar
  • 24 Liron F. Fosse C. Pernolet A. Roulland E. J. Org. Chem.  2007,  72:  2220 
    CrossrefGoogle Scholar
  • 25 Roulland E. Angew. Chem. Int. Ed.  2008,  47:  3762 
    CrossrefGoogle Scholar
  • For other syntheses of haterumalide NA, see:
  • 26a Kigoshi H. Kita M. Ogawa S. Itoh M. Uemura D. Org. Lett.  2003,  5:  957 
    Google Scholar
  • 26b Gu Y. Snider BB. Org. Lett.  2003,  5:  4385 
    Google Scholar
  • 26c Hoye TR. Wang J. J. Am. Chem. Soc.  2005,  127:  6950 
    Google Scholar
  • 26d Hayakawa I. Ueda M. Yamuara M. Ikeda Y. Suzuki Y. Yoshizato K. Kigoshi H. Org. Lett.  2008,  10:  1859 
    Google Scholar
  • 27 Tennyson RL. Cortez GS. Galicia HJ. Kreiman CR. Thompson CM. Romo D. Org. Lett.  2002,  4:  533 
    CrossrefPubMedGoogle Scholar
  • 29 Li J. Xu X. Zhang Y. Tetrahedron Lett.  2003,  44:  9349 
    CrossrefGoogle Scholar
12

Propargyl acrylate did not react with olefin 11 by ene-yne cross-metathesis [Grubbs II (5-10 mol%), CH2Cl2, reflux, 4-8 h; trace of lactones 10a,c detected by TLC] and did also not produce the γ-methylene α,β-unaturated lactone 12 by ene-yne RCM (vide infra).

19

( E )-5-[( tert -Butyldiphenylsilyloxy)propylidene]-5,6-dihydropyran-2-one (10a) IR: 1721, 1427, 1391, 1248, 1221, 1199, 1091, 1027, 820, 786, 733, 700, 613 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.64-7.62 (m, 4 H), 7.46-7.36 (m, 6 H), 7.21 (dd, J = 9.9, 1.1 Hz, 1 H), 5.90 (dd, J = 9.9, 1.8 Hz, 1 H), 5.76 (m, 1 H), 4.83 (m, app. br d, J = 1.2 Hz, 2 H), 3.74 (t, J = 6.3 Hz, 2 H), 2.46-2.41 (m, 2 H), 1.04 (s, 9 H). ¹³C NMR (100 MHz, CDCl3): δ = 164.1 (s), 139.0 (d), 135.5 (d, 4 C), 133.4 (s, 3 C), 131.7 (d), 129.8 (d, 2 C), 127.7 (d, 4 C), 119.0 (d), 71.1 (t), 62.5 (t), 31.0 (t), 26.8 (q, 3 C), 19.1 (s). MS (EI, 70 eV): m/z (%) = 377 (1) [M - Me+], 355 (64) [M - t-Bu+], 307 (9), 306 (27), 305 (100), 257 (19), 227 (17), 200 (15), 199 (80), 197 (16), 183 (13), 181 (18), 167 (7), 135 (18), 105(10), 91 (6), 77 (12). HRMS-FAB: m/z calcd for C24H28NaO3Si [M + Na+]: 415.1699; found: 415.1692.

21

( Z )-5-[( tert -Butyldiphenylsilyloxy)propylidene]-5,6-dihydropyran-2-one (10c) IR: 1719, 1644, 1427, 1221, 1104, 937, 820, 738, 700, 613 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 7.65-7.62 (m, 4 H), 7.46-7.37 (m, 6 H), 6.92 (d, J = 9.7 Hz, 1 H), 5.85-5.81 (m, 2 H), 5.00 (m, app. br s, 2 H), 3.75 (t, J = 6.2 Hz, 2 H), 2.33 (dt, app. q, J = 6.4 Hz, 2 H), 1.04 (s, 9 H). ¹³C NMR (100 MHz, CDCl3): δ = 163.7 (s), 145.0 (d), 135.5 (d, 4 C), 133.8 (d), 133.3 (s, 2 C), 129.8 (d, 2 C), 128.7 (s), 127.7 (d, 4 C), 116.7 (d), 66.6 (t), 62.3 (t), 31.6 (t), 26.8 (q, 3 C), 19.1 (s). HRMS-FAB: m/z calcd for C24H28NaO3Si [M + Na+]: 415.1699; found: 415.1693.

22

For a similar observation in the cross-metathesis between 1,2-substituted-1,3-butadienes and 1-alkenes, see ref. 14a.

28

The geometric isomers (Z/E = 95:5) were easily separated by flash chromatography.

30

( E )-3-(4,4-Dichlorobut-3-enylidene)-6-methoxy-3,6-dihydro-2 H -pyran (22)
IR: 1684, 1619, 1446, 1384, 1300, 1187, 1158, 1103, 956, 872, 749 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 6.61 (d, J = 10.2 Hz, 1 H), 5.95-5.83 (m, 1 H), 5.82 (t, J = 7.4 Hz, 1 H), 5.29 (t, J = 7.8 Hz, 1 H), 4.91 (d, J = 2.8 Hz, 1 H), 4.49 (d, AB syst, J = 13.0 Hz, 1 H), 3.99 (d, AB syst, J = 13.0 Hz, 1 H), 3.45 (s, 3 H), 3.02 (app. td, J = 7.6, 1.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 130.9 (s), 127.0 (d), 126.6 (d), 123.7 (d), 121.7 (d), 121.3 (s), 95.5 (d), 62.6 (t), 55.4 (q), 27.2 (t). HRMS-FAB: m/z calcd for C10H12 ³5Cl2NaO2 [M + Na+]: 257.01066; found: 257.01065.