pubs.acs.org/joc
as rifamycin S,6 zincophorin,7 6-deoxyerythronolide B,8
Synthesis of (E,Z)-1-Alkoxy-3-acyloxy-2-
methylpenta-1,3-dienes via Danishefsky-Type Dienes
or O-Acylation of Enones
discodermolide,9 epothilones,10 migrastatin,11 (þ)-prelac-
tone C and (þ)-9-deoxygoniopyrone,12 phorboxazoles,13
and dictyostatin.14 Their synthesis involves a hetero-
Diels-Alder addition of aldehydes,15,16 in contrast to the
one of yohimbine congeners17 applying hetero-Diels-Alder
addition of imines.18-20
Sylvain Laclef,†,§ Claudia J. Exner,†,§ Maris Turks,‡
Valeria Videtta,§ and Pierre Vogel*,§
§Laboratory of Glycochemistry and Asymmetric Synthesis
(LGSA), Swiss Federal Institute of Technology (EPFL),
Batochime, CH-1015 Lausanne, Switzerland. †These authors
contributed equally to this work. ‡Present address: Faculty of
Material Science and Applied Chemistry, Riga Technical
University, LV-1048 Riga, Latvia
In 1997 our group uncovered a new C-C bond forming
reaction cascade that condenses butadiene-1-yl ethers 1,
enoxysilanes 2, and SO2 to generate γ,δ-unsaturated silyl-
sulfinates 3. After desilylation, the corresponding sulfinic
(8) Myles, D. C.; Danishefsky, S. J.; Schulte, G. J. Org. Chem. 1990, 55,
1636–1648.
(9) (a) Yang, G.; Myles, D. C. Tetrahedron Lett. 1994, 35, 2503–2504. (b)
Harried, S. S.; Lee, C. P.; Yang, G.; Lee, T. I. H.; Myles, D. C. J. Org. Chem.
2003, 68, 6646–6660.
(10) (a) Bertinato, P.; Sorensen, E. J.; Meng, D.; Danishefsky, S. J. J. Org.
Chem. 1996, 61, 8000–8001. (b) Meng, D.; Bertinato, P.; Balog, A.; Su, D.-S.;
Kamenecka, T.; Sorensen, E. J.; Danishefsky, S. J. J. Am. Chem. Soc. 1997,
119, 10073–10092. (c) Biswas, K.; Lin, H.; Njardarson, J. T.; Chappell, M.
D.; Chou, T.-C.; Guan, Y.; Tong, W. P.; He, L.; Horwitz, S. B.; Danishefsky,
S. J. J. Am. Chem. Soc. 2002, 124, 9825–9832.
Received September 9, 2009
(11) (a) Gaul, C.; Danishefsky, S. J. Tetrahedron Lett. 2002, 43, 9039–
9042. (b) Gaul, C.; Njardarson, J. T.; Danishefsky, S. J. J. Am. Chem. Soc.
2003, 125, 6042–6043. (c) Gaul, C.; Njardarson, J. T.; Shan, D.; Dorn, D. C.;
Wu, K.-D.; Tong, W. P.; Huang, X.-Y.; Moore, M. A. S.; Danishefsky, S. J.
J. Am. Chem. Soc. 2004, 126, 11326–11337.
(12) Yamashita, Y.; Saito, S.; Ishitani, H.; Kobayashi, S. J. Am. Chem.
Soc. 2003, 125, 3793–3798.
(13) Lucas, B. S.; Luther, L. M.; Burke, S. D. J. Org. Chem. 2005, 70,
3757–3760.
(14) Dilger, A. K.; Gopalsamuthiram, V.; Burke, S. D. J. Am. Chem. Soc.
2007, 129, 16273–16277.
1-Alkoxy-2-methyl-3-acyloxy-(E,E)-penta-1,3-dienes have
been prepared applying among others a modified Danishefsky’s
general method, including chiral, racemic, and achiral
derivatives.
(15) (a) Larson, E. R.; Danishefsky, S. J. Am. Chem. Soc. 1982, 104, 6458–
6460. (b) Gaul, C.; Njardarson, J. T.; Danishefsky, S. J. J. Am. Chem. Soc.
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J. Am. Chem. Soc. 1984, 106, 2456–2458.
Danishefsky’s dienes (1,3-dioxy-substituted 1,3-dienes)
are extremely useful reagents for the construction of natural
products and analogues of biological interest.1,2 Especially
interesting are (E,Z)-1-alkoxy-3-trialkylsilyloxy-2-methyl-
penta-1,3-dienes3,4 used to prepare polypropionates5 such
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Tetrahedron Lett. 1983, 24, 3451–3454. (b) Maruoka, K.; Itoh, T.; Shirasaka,
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K.; Maruyama, T.; Mouri, M.; Yamamoto, H. Tetrahedron 1994, 50, 979–
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Yao, S.; Roberson, M.; Reichel, F.; Hazell, R. G.; Jorgensen, K. A. J. Org.
Chem. 1999, 64, 6677–6687. (i) Simonsen, K. B.; Svenstrup, N.; Roberson,
M.; Jorgensen, K. A. Chem.;Eur. J. 2000, 6, 123–128. (j) Yamashita, Y.;
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Anada, M.; Washio, T.; Shimada, N.; Kitagaki, S.; Nakajima, M.; Shiro, M.;
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M.; Doyle, M. P.; Hedberg, C.; Hu, W.; Holmstrom, A. Synlett 2004, 2425–
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K. A. J. Org. Chem. 2007, 72, 240–245. (n) Yu, Z.; Liu, X.; Dong, Z.; Xie, M.;
Feng, X. Angew. Chem., Int. Ed. 2008, 47, 1308–1311. (o) Scettri, A.;
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8882 J. Org. Chem. 2009, 74, 8882–8885
Published on Web 10/20/2009
DOI: 10.1021/jo901878b
r
2009 American Chemical Society