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LETTER
(4) (a) Houdai, T.; Matsuoka, S.; Morsy, N.; Matsumori, N.;
To a solution of the appropriate dibenzoate in a 3:1 mixture of THF–
MeOH (0.016 M) was added Na2HPO4 (7.5 equiv) at r.t. The mix-
ture was cooled to –20 °C and treated with sodium–mercury amal-
gam (6% Na, 10.8 equiv). After 5 h at –20 °C, the mixture was
filtered (G3 sinter), washed with Et2O (40 mL per mmol), and the
organic layer was successively washed with H2O and brine. The
aqueous phase was extracted with Et2O and the combined organic
extracts were washed with brine, dried over Na2SO4, filtered, and
concentrated under reduced pressure.
Satake, M.; Murata, M. Tetrahedron 2005, 61, 2795.
(b) Paul, G. K.; Matsumori, N.; Nonoki, K.; Sasaki, M.;
Murata, M.; Tachibana, K. In Harmful and Toxic Algal
Blooms.; Yasumoto, T.; Oshima, Y.; Fukuyo, Y., Eds.;
Proceedings of the Seventh International Conference on
Toxic Phytoplankton, UNESCO: Sendai, Japan, 1996, 503.
(5) (a) Murata, M.; Matsuoka, S.; Matsumori, N.; Paul, G. K.;
Tachibana, K. J. Am. Chem. Soc. 1999, 121, 870.
(b) Matsumori, N.; Kaneno, D.; Murata, M.; Nakamura, H.;
Tachibana, K. J. Org. Chem. 1999, 64, 866.
(6) (a) Paquette, L. A.; Chang, S.-K. Org. Lett. 2005, 7, 3111.
(b) Chang, S.-K.; Paquette, L. A. Synlett 2005, 2915.
(c) Bedorre, M. W.; Chang, S.-K.; Paquette, L. A. Org. Lett.
2007, 9, 513.
(7) (a) de Vicente, J.; Betzemeier, B.; Rychnovsky, S. D. Org.
Lett. 2005, 7, 1853. (b) de Vicente, J.; Huckins, J. R.;
Rychnovsky, S. D. Angew. Chem. Int. Ed. 2006, 45, 7258.
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(b) Hicks, J. D.; Flamme, E. D.; Roush, W. R. Org. Lett.
2005, 7, 5509.
(4E,6E,8E)-1-(tert-Butyldiphenylsilanyloxy)12-(tert-butyldi-
methylsilanyloxy)dodeca-4,6,8-triene (14)
According to the general procedure for the reductive elimination,
561 mg (79%) of all-trans-triene 14 was obtained starting from
dibenzoate 4 (1.03 g, 1.30 mmol) after purification of the crude
product by flash column chromatography on silica gel (Et2O–cyclo-
hexane, 1:40): Rf = 0.80 (EtOAc–cyclohexane, 1:10). IR (ATR):
n = 2930, 2857, 1104, 835, 699 cm–1. 1H NMR (400 MHz, CDCl3):
d = 0.06 (s, 6 H), 0.91 (s, 9 H), 1.06 (s, 9 H), 1.59–1.69 (m, 4 H),
2.13–2.23 (m, 4 H), 3.62 (t, J = 6.4 Hz, 2 H), 3.68 (t, J = 6.3 Hz, 2
H), 5.59–5.71 (m, 2 H, H-56, H-61), 6.01–6.18 (m, 4 H, H-57, H-
58, H-59, H-60), 7.36–7.45 (m, 6 H), 7.66–7.68 (m, 4 H). 13C NMR
(75 MHz, CDCl3): d = –5.27 (q), 18.34 (s), 19.24 (s), 25.97 (q),
26.88 (q), 29.07 (t), 32.22 (t), 32.45 (t), 62.51 (t), 63.20 (t), 127.59
(d), 129.50 (d), 130.76 (d), 130.79 (d), 130.85 (d), 130.87 (d),
133.77 (d), 134.06 (s), 135.57 (d). Anal. Calcd for C34H52O2Si2: C,
74.39; H, 9.55. Found: C, 74.51; H, 9.692.
(9) BouzBouz, S.; Cossy, J. Org. Lett. 2001, 7, 1451.
(10) Dubost, C.; Markó Bryans, J. Tetrahedron Lett. 2005, 46,
4005.
(11) Cossy, J.; Tsuchiya, T.; Ferrié, L.; Reymond, S.; Kreuzer, T.;
Colobert, F.; Jourdain, P.; Markó, I. Synlett 2007, in press.
(12) (a) Solladié, G.; Urbano, A.; Stone, G. B. Synlett 1993, 548.
(b) Solladié, G.; Urbano, A.; Stone, G. B. Tetrahedron Lett.
1993, 34, 6489. (c) Solladié, G.; Colobert, F.; Kalaï, C.
Tetrahedron Lett. 2000, 41, 4197. (d) Solladié, G.; Kalaï,
C.; Adamy, M.; Colobert, F. Tetrahedron Lett. 1997, 39,
6917. (e) Solladié, G.; Somny, F.; Colobert, F. Tetrahedron:
Asymmetry 1997, 8, 801. (f) Solladié, G.; Adamy, M.;
Colobert, F. J. Org. Chem. 1996, 61, 4369.
(4E,6E,8E,12E)-1-(tert-Butyldiphenylsilanyloxy)pentadeca-
4,6,8,12,14-pentaene (2)
According to the general procedure for the reductive elimination, 71
mg (70%) of the polyene fragment 2 was obtained starting from
dibenzoate 3 (155 g, 0.22 mmol) after purification of the crude
product by flash column chromatography on silica gel (Et2O–cyclo-
hexane, 1:30): Rf = 0.48 (EtOAc–cyclohexane, 1:30). IR (ATR):
(13) Mc Dougal, P. G.; Rico, J. G.; Oh, Y.-I.; Condom, B. D.
J. Org. Chem. 1986, 51, 3388.
n = 2930, 1428, 1106, 994, 700, 687 cm–1. H NMR (300 MHz,
1
CDCl3): d = 1.06 (s, 9 H), 1.58–1.70 (m, 2 H), 2.04–2.36 (m, 6 H),
3.67 (t, J = 6.3 Hz, 2 H), 4.98 (dd, J = 10.1, 1.5 Hz, 1 H, H-67), 5.11
(dd, J = 16.9, 1.6 Hz, 1 H, H-67), 5.33–5.87 (m, 3 H, H-56, H-61,
H-64), 5.97–6.18 (m, 5 H, H-57, H-58, H-59, H-60, H-65), 6.31 (td,
J = 10.2, 16.8 Hz, 1 H, H-66), 7.35–7.46 (m, 6 H), 7.66–7.69 (m, 4
H). 13C NMR (75 MHz, CDCl3): d = 19.24 (s), 26.88 (q), 29.07 (t),
32.21 (t), 32.38 (t), 32.46 (t), 63.20 (t), 115.02 (t), 127.59 (d),
129.51 (d), 130.75 (d), 130.99 (d), 131.16 (d), 131.38 (d), 133.16
(d), 133.98 (d), 134.05 (s), 134.35 (d), 135.58 (d), 137.18 (d).
HRMS (ESI+): m/z calcd for C31H40NaOSi [M + Na+]: 479.2741;
found: 479.2751.
(14) Nacro, K.; Baltas, M.; Gorrichon, L. Tetrahedron 1999, 55,
14013.
(15) Omura, K.; Swern, D. Tetrahedron 1978, 34, 1651.
(16) Taillier, C.; Gille, B.; Bellosta, V.; Cossy, J. J. Org. Chem.
2005, 70, 2097.
(17) (a) Holmes, A. B.; Jennings-White, C. L. D.; Schulthess, A.
H.; Akinde, B.; Walton, D. R. M. J. Chem. Soc., Chem.
Commun. 1979, 840. (b) Kraus, G. A.; Bae, J. Tetrahedron
Lett. 2003, 44, 5505. (c) For a review, see: Kusumoto, T.;
Hiyama, T. Rev. Heteroat. Chem. 1994, 11, 143.
(18) (a) Boland, W.; Schröer, N.; Sieler, C.; Feigel, N. Helv.
Chim. Acta 1987, 70, 1025. (b) See ref. 12b and 12e.
(19) The all-trans configuration of the triene moiety was
confirmed by performing 1H NMR irradiation experiments
on the corresponding symmetrical diol, which is easily
available by deprotection of the silyl groups starting from
diol 14. The analysis of 1H-decoupled NMR spectra resulted
in a coupling constant consistent with E-olefins (J = 14.1
Hz).
Acknowledgment
Financial support of this work by Prof. Jean-Yves Lallemand at the
ICSN (Institut de Chimie des Substances Naturelles, Gif-sur-
Yvette) and by the CNRS (UMR 7509) is gratefully acknowledged.
Special thanks are due to Chung-Meng Chao (ECPM Strasbourg)
for his experimental help during his master project.
(20) Prakash, C.; Saleh, S.; Blair, I. A. Tetrahedron Lett. 1989,
30, 19.
(21) Jung, M. E.; Piizzi, G. J. Org. Chem. 2002, 67, 3911.
(22) Takai, S.; Isobe, M. Org. Lett. 2002, 4, 1183.
(23) (a) Gómez, A. M.; López, J. C.; Fraser-Reid, B. J. Org.
Chem. 1995, 60, 3859. (b) Hong, S.-P.; Yoon, S.-J.; Yu,
B.-C. Tetrahedron Lett. 2005, 46, 779. (c) van Boxtel, L. J.;
Körbe, S.; Noltemeyer, M.; de Meijere, A. Eur. J. Org.
Chem. 2001, 2283.
References and Notes
(1) (a) Shimizu, Y. Chem. Rev. 1993, 1685. (b) Yasumoto, T.;
Murata, M. Chem. Rev. 1193, 1897.
(2) Echigoya, R.; Rhodes, L.; Oshima, Y.; Satake, M. Harmful
Algae 2005, 4, 383.
(3) Satake, M.; Murata, M.; Yasumoto, T. J. Am. Chem. Soc.
1991, 113, 9859.
(24) (a) Amafor, M.; Ariza, X.; Garcia, J.; Sevilla, S. Org. Lett.
2002, 4, 4511. (b) See ref. 12a.
Synlett 2007, No. 15, 2351–2354 © Thieme Stuttgart · New York