I. Garcı´a et al. / Tetrahedron Letters 47 (2006) 1333–1335
1335
Iwabuchi, Y.; Irie, H.; Hatakeyama, S. Heterocycles 2000,
52, 525–528; (f) Lukesh, J. M.; Donaldson, W. A. Tetra-
hedron: Asymmetry 2003, 14, 757–762.
6.8%
H
OH
8.1%
´
´
4. (a) Fall, Y.; Gomez, G.; Fernandez, C. Tetrahedron Lett.
H
1999, 40, 8307–8308; (b) Fall, Y.; Vidal, B.; Alonso, D.;
H3C
1.1%
O
OTBS
´
Gomez, G. Tetrahedron Lett. 2003, 44, 4467–4469; (c)
H
0.5%
´
´
´
Perez, M.; Canoa, P.; Gomez, G.; Teran, C.; Fall, Y.
Tetrahedron Lett. 2004, 45, 5207–5209; (d) Alonso, D.;
´
´
Perez, M.; Gomez, G.; Covelo, B.; Fall, Y. Tetrahedron
13
´
´
2005, 61, 2021–2026; (e) Perez, M.; Canoa, P.; Gomez, G.;
Teijeira, M.; Fall, Y. Synthesis 2005, 411–414.
5. All new compounds exhibited satisfactory 1H and 13C
NMR, analytical, and/or high resolution mass spectral
data.
Figure 2. NOE correlations for 13.
for the final TBAF deprotection step which afforded
(+)-decarestrictine L (2) which was spectroscopically
identical to the natural product.1,3f
´
6. Perez-Sestelo, J.; Mascarenas, J. L.; Castedo, L.; Mourino,
˜
˜
A. J. Org. Chem. 1993, 58, 118–123.
25
7. (a) Compound 1: ½aꢁD +0.5 (c 0.012, MeOH); 1H NMR
(400 MHz, CDCl3), d: 7.70 (4H, d, J = 6.94), 7.46–7.40
(6H, m), 7.39–7.33 (1H, m), 6.25 (1H, dd, J = 2.04, 2.84),
5.88 (1H, d, J = 2.84), 3.94 (1H, q, J = 5.93), 2.72–2.66
(2H, m), 1.87–1.77 (2H, m), 1.10 (3H, d, J = 6.14),
1.08 (9H, s); 13C NMR (100 MHz, CDCl3), d: 156.23 (C),
140.64 (CH), 135.86 (CH), 134.76 (C), 129.50 (CH), 127.50
(CH), 110.00 (CH), 104.44 (CH), 68.87 (CH), 37.46 (CH2),
27.02 (CH3-tBu), 23.81 (CH3), 23.12 (CH2), 19.29 (C-tBu);
HRMS (FAB+) calcd for C24H29O2Si 377.1937, found
377.1951; (b) Compound 12: 1H NMR (400 MHz, CDCl3),
d: 3.92 (1H, s), 3.85–3.80 (1H, m), 3.76–3.70 (1H, m), 3.39
(1H, m), 3.32–3.27 (1H, m), 3.16–3.11 (1H, m), 2.08–2.05
(1H, m), 1.89–1.83 (2H, m), 1.67 (1H, m), 1.47–1.18 (2H,
m), 1.14 (3H, d, J = 5.98), 0.89 (9H, s), 0.07 (6H, s); 13C
NMR (100 MHz, CDCl3), d: 81.15 (CH), 73.44 (CH), 70.21
(CH), 60.38 (CH2), 37.59 (CH2), 32.90 (CH2), 32.09 (CH2),
25.84 (CH3-tBu), 21.46 (CH3), 18.21 (C-tBu), ꢀ5.47
(CH3Si), ꢀ5.55 (CH3Si); HRMS (FAB+) calcd for
C14H31O3Si 275.2042, found 275.2049; (c) Compound 13:
1H NMR (400 MHz, CDCl3), d: 3.91–3.85 (2H, m), 3.79–
3.45 (3H, m), 2.80 (1H, s), 1.95–1.84 (2H, m), 1.83–1.76
(1H, m), 1.75–1.64 (1H, m), 1.60–1.53 (1H, m), 1.40–
1.24 (1H, m), 1.17 (3H, d, J = 6.52), 0.89 (9H, s), 0.06 (6H,
s); 13C NMR (100 MHz, CDCl3), d: 74.25 (CH), 67.19
(CH), 66.88 (CH), 60.19 (CH2), 32.34 (CH2), 27.88 (CH2),
26.57 (CH2), 26.26 (CH3-tBu), 18.84 (CH4), 18.24 (C-tBu),
ꢀ5.46 (CH3Si); HRMS (FAB+) calcd for C14H31O3Si
In conclusion, a new and efficient method for the enan-
tioselective synthesis of (+)-decarestrictine L (2) from
commercially available chiral hydroxyester
3
is
described. This synthesis enlarges the scope of our newly
developed methodology for the synthesis of oxacyclic
systems. The use of this methodology for the synthesis
of various natural products is now under way in our
laboratories.
Acknowledgements
This work was supported by a grant from the Xunta de
Galicia (PGIDIT04BTF301031PR). We also thank the
NMR service of the CACTI, University of Vigo, for
NMR studies. M.T. thanks the Xunta de Galicia for a
Parga Pondal contract.
References and notes
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25
275.2042, found 275.2049; (d) Compound 15: ½aꢁD
1
2. (a) Go¨hrt, A.; Zeeck, A.; Huetter, K.; Kirssch, R.; Kluge,
¨
+11.61 (c 0.018, MeOH); H NMR (400 MHz, CDCl3), d:
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65.03 (CH), 40.71 (CH2), 31.57 (CH2), 29.70, 27.46.77
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