Efficient Syntheses of the Polyene Fragments Present in Amphidinols

Janine Cossy; Tomoki Tsuchiya; Laurent Ferrié; Sébastien Reymond; Thomas Kreuzer; Françoise Colobert; Pierre Jourdain; István E. Markó

doi:10.1055/s-2007-984910

LETTER

Efficient Syntheses of the Polyene Fragments Present in Amphidinols

Janine Cossy*^a, Tomoki Tsuchiya^a, Laurent Ferrié^a, Sébastien Reymond^a, Thomas Kreuzer^b, Françoise Colobert^b, Pierre Jourdain^c, István E. Markó^c
^a Laboratoire de Chimie Organique, ESPCI, CNRS, 10 Rue Vauquelin, 75231, Paris Cedex 05, France
Fax: +33(1)40794660; e-Mail: janine.cossy@espci.fr;
^b Laboratoire de Stéréochimie, Université Louis Pasteur, ECPM, CNRS, 25 Rue Becquerel, 67087 Strasbourg Cedex 2, France
^c Université Catholique de Louvain, Unité de Chimie Organique et Médicinale, Bâtiment Lavoisier, Place Louis Pasteur 1, 1348 Louvain-la Neuve, Belgium

Abstract

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Abstract

The C53-C67 and C53-C65 polyene fragments of amphidinols have been synthesized in an efficient and convergent fashion from sorbic acid in good overall yields (30-31%) by employing a chemoselective cross-metathesis of a Weinreb amide and a Julia-Kocienski olefination as the key steps.

Key words

cross-metathesis - Julia-Kocienski olefination - amphidinols - polyenes

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References

References and Notes

1 Satake M. Murata M. Yasumoto M. Fujita T. Naoki H. J. Am. Chem. Soc. 1991, 113: 9859

2a Paul GK. Matsumori N. Murata M. Tachibana K. Tetrahedron Lett. 1995, 36: 6279

2b Houdai T. Matsuoka S. Murata M. Satake M. Ota S. Oshima Y. Rhodes LL. Tetrahedron 2001, 57: 5551

2c Murata M. Matsuoka S. Matsumori N. Paul GK. Tachibana K. J. Am. Chem. Soc. 1999, 121: 870

2d Paul GK. Matsumori N. Konoki K. Murata M. Tachibana K. J. Mar. Biotech. 1997, 5: 124

2e Paul GK. Matsumori N. Konoki K. Sasaki M. Murata M. Tachibana K. In Harmful and Toxic Algal Blooms. Proceedings of Seventh International Conference on Toxic Phytoplankton Yasumoto T. Oshima Y. Fukuyo Y. UNESCO; Sendai / Japan: 1996. p.503-506

2f Echigoya R. Rhodes L. Oshima Y. Satake M. Harmful Algae 2005, 4: 383

2g Morsy N. Houdai T. Matsuoka S. Matsumori N. Adachi S. Oishi T. Murata M. Iwashita T. Fujita T. Bioorg. Med. Chem. 2006, 14: 6548

3 Chang S.-K. Paquette LA. Synlett 2005, 2915

4 Hicks JD. Flamme EM. Roush WR. Org. Lett. 2005, 7: 5509

5 de Vicente J. Huckins JR. Rychnovsky SD. Angew. Chem. Int. Ed. 2006, 45: 7258

6 Ferrié L. Amans D. Reymond S. Bellosta V. Capdevielle P. Cossy J. J. Organomet. Chem. 2006, 691: 5456

7 Ley SV. Cox LR. Meek G. Metten K.-H. Piqué C. Worrall JM. J. Chem. Soc., Perkin Trans. 1 1997, 3299

8 Spino C. Crawford J. Tetrahedron Lett. 1994, 35: 5559

9 Ware RW. Day CS. King SB. J. Org. Chem. 2002, 67: 6174

10 Trost BM. Crawley ML. Chem. Eur. J. 2004, 10: 2237

11 Blakemore PR. Cole WJ. Kocienski PJ. Morley A. Synlett 1998, 26

12

tert -Butyl-dimethyl-{[(4 E ,6 E ,8 E ,12 E )-pentadeca-4,6,8,12,14-pentaenyl]oxy}-silane (8)
A 9:1 mixture of inseparable E- and Z-isomers; R _f = 0.63 (PE-Et₂O, 9:1). IR (neat): 3012, 2927, 2855, 1651, 1603, 1253, 1100 cm^-1. ¹H NMR (400 MHz, C₆D₆): δ = 6.29 (dtd, J = 17.0, 10.2, 0.7 Hz, 1 H), 6.18-5.97 (m, 5 H), 5.62 (m, 1 H), 5.54 (dt, J = 14.5, 6.7 Hz, 2 H), 5.06 (d, J = 17.0 Hz, 1 H), 4.93 (d, J = 10.1 Hz, 1 H), 3.51 (t, J = 6.2 Hz, 2 H), 2.14 (td, J = 7.4, 7.1 Hz, 2 H), 2.05-1.99 (m, 4 H), 1.56 (tt, J = 7.6, 6.3 Hz, 2 H), 1.00-0.96 (m, 9 H), 0.06-0.03 (m, 6 H). ¹³C NMR (100 MHz, C₆D₆): δ = 137.6 (d), 134.4 (d), 134.0 (d), 133.2 (d), 132.0 (d), 131.7 (d), 131.6 (d), 131.5 (d), 131.4 (d), 115.2 (t), 62.5 (t), 32.5 (t), 32.8 (t), 32.7 (t), 29.5 (t), 26.1 (q), 18.5 (s), -5.2 (q). MS (EI): m/z = 322 (7) [M⁺], 275 (20), 265 (20), 133 (100), 67 (37). ESI-HRMS: m/z calcd for C₂₁H₃₆OSi + Na⁺: 355.2428; found: 355.2429.

13

tert -Butyl-dimethyl-{[(4 E ,6 E ,8 E )-tetradeca-4,6,8,12-tetraenyl]oxy}-silane (10)
R _f = 0.53 (PE-Et₂O, 98:2). IR (neat): 3013, 2928, 2856, 1641, 1101, 993 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.12-6.01 (m, 4 H), 5.81 (ddt, J = 17.1, 10.3, 6.4 Hz, 1 H), 5.72-5.61 (m, 2 H), 5.02 (ddd, J = 17.1, 3.4, 1.5 Hz, 1 H), 4.97 (m, 1 H), 3.61 (t, J = 6.4 Hz, 2 H), 2.21-2.11 (m, 6 H), 1.64-1.54 (m, 2 H), 0.91-0.87 (m, 9 H), 0.06-0.02 (m, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 138.2 (d), 134.0(d), 133.4 (d), 131.4 (d), 131.1 (d), 130.9 (d), 130.8 (d), 114.8 (t), 62.5 (t), 33.5 (t), 32.4 (t), 32.2 (t), 29.1 (t), 26.0 (q), 18.4 (s), -5.3 (q). MS (EI): m/z = 306 (6) [M⁺], 249 (74), 175 (10), 133 (87), 131 (46), 91 (100), 81 (11), 75 (96), 55 (14). ESI-HRMS: m/z calcd for C₁₉H₃₄OSi + Na⁺: 329.2271; found: 329.2271.