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A. Ishiwata et al.
LETTER
(3 eq), MeOH, -20~rt, 12 h (81%, in 2 steps); 3) (MeO)2POMe
(1.6 eq), n-BuLi (1.5 eq), THF, –78~–50°C (96%).
(14) M. A. Blanchette, W. Choy, J. T. Davis, A. P. Essenfeld, S.
Masamune, W. R. Roush, T. Sakai, Tetrahedron Lett., 1984,
25, 2183.
Further study directed toward total synthesis of 1 includ-
ing the epimerization at C31 is currently underway in our
laboratory.
(15) H. Köster and N. D. Shinha, Tetrahedron Lett., 1982, 23,
2641.
(16) O. Mitsunobu, Synthesis, 1981, 1.
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Oxford, 1991; Vol. 5, p 513; W. R. Roush, B. B. Brown, J. Am.
Chem. Soc., 1993, 115, 2268.
Acknowledgement
We are grateful to Dr. Masako Ueno, and Mr. Kazuo Sasaki (Instru-
mental Analysis Center for Chemistry, Tohoku University) for their
assistance in NMR measurement. This work was supported in part
by a grant from the Ministry of Education, Science, Sports and Cul-
ture, Japan.
(18) a) K. Maruoka, K. Nonoshita, H. Yamamoto, Synth Commun,
1988, 18, 1453. b) H. Lamy-Schelkens, D. Giomi, L. Ghosez,
Tetrahedron Lett., 1989, 30, 5887.
References and Notes
(19) 14 ([a]D25 18.8° (c 0.80, CHCl3)): IR(film) 2954, 2866, 1723,
1613, 1516, 1464, 1251, 1189, 1112, 1031, 884, 837, 758, 679
(cm–1); 1H NMR ((CD3)2CO, 600 MHz) d 7.28 (5 H, m,
PhCH2O), 7.23 (2 H, m, MPM), 6.85 (2 H, d, J = 8.6 Hz,
MPM), 5.39 (1 H, brs, H32), 4.67 (1 H, brd, J = 12.0, 8.0 Hz,
H28), 4.69 (1 H, d, J = 11.2 Hz, MPM), 4.57 (1 H, d, J = 11.2
Hz, MPM), 4.35 (1 H, d, J = 11.9 Hz, PhCH2O), 4.33 (1 H, d,
J = 11.9 Hz, PhCH2O), 4.09 (1 H, brs, H30), 4.00 (1 H, brd, J
= 12.0 Hz, H28), 3.82 (1 H, d, J = 12.0 Hz, H34), 3.79 (1 H, d,
J = 12.0 Hz, H34), 3.72 (3 H, s, MPM), 3.56 (1 H, dd, J = 9.8,
7.5 Hz, H1), 3.52 (1 H, bt, J = 7.5, 1.5 Hz, H29), 3.46 (1 H, dd,
J = 9.8, 6.4 Hz, H1), 2.64 (1 H, brs, H31), 2.47 (1 H, m, H4),
2.29 (2 H, m, H35, H39), 1.97 (1 H, m, H3), 1.92 (1 H, m,
H35), 1.58 (1 H, qdd, J = 7.0, 7.0, 3.2 Hz, H2), 1.45 (2 H, m,
H4, H39), 1.10–1.00 (21 H, m, SiCH(CH3)2), 0.88 (9 H, m,
SiC(CH3)3), 0.77 (3 H, d, J = 7.0 Hz, C2(CH3)), 0.74 (3 H, d,
J = 7.0 Hz, C3(CH3)), 0.07 (3 H, s, SiCH3), 0.05 (3 H, s,
SiCH3). 13C NMR ((CD3)2CO, 150 MHz) d >150 (C6=O,
MPM), 139.75 (Bn), 137.72 (C33), 131.14 (MPM), 130.36
(MPM), 128.99 (Bn), 128.46 (Bn), 128.13 (Bn), 124.22 (C32),
114.42 (MPM), 78.08 (C29), 77.36 (C30), 74.35 (C34), 74.29
(MPM), 72.09 (Bn), 67.28 (C1), 64.70 (C28), 55.44 (MeO),
50.90 (C5), 47.36 (C31), 43.82 (C4), 43.46 (C2), 43.38 (C3),
33.06 (C35), 28.48 (SiC(CH3)3), 26.44 (SiC(CH3)3), 24.66
(C39), 18.79 (SiC(CH3)3), 18.41 (SiCH(CH3)2), 15.21 (C3-
CH3), 12.76 (SiCH(CH3)2), 11.82 (C2-CH3), –4.45 (SiCH3).
(1) a) D. Uemura, T. Chou, T. Haino, A. Nagatsu, S. Fukuzawa,
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H. F. Kaspar, T. Yasumoto, Tetrahedron Lett., 1995, 36, 7093.
b) M. Stewart, J. W. Blunt, M. H. G. Munro, W. T. Robinson,
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Peng, R. W. Xie, Zhongguo Haiyang Yaowu (Chinese J. of
Marine Drugs), 1990, 33, 33.
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603.
(8) Prepared from methyl (R)-(-)-hydroxy-2-methylpropionate as
follows: 1) TIPSCl, imidazole, DMF (83%); 2) DIBAL-H,
CH2Cl2 (92%); 3) Ph3P=CHCO2Me, toluene (95%); 4)
DIBAL-H, CH2Cl2 (83%); 5) Ti(Oi-Pr)4 (cat.), (-)-diethyl
tartrate (cat.), t-BuOOH, molecular sieves 4A, CH2Cl2 (95%).
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(10) a) A. Eschenmoser, Angew. Chem. Int. Ed. Engl., 1971, 10,
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Yanase, M. Suzuki, Y. Iwabuchi, Chem. Lett., 1989, 1283
(11) Prepared from D-glucose as follows: 1) D-glucose, p-
anisaldehyde (2 eq), p-TsOH (cat.), DMF; 2) NaIO4 (3 eq),
MeOH; 3) NaBH4 (2 eq), MeOH in 25% yield (3 steps).
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24, 4037.
(13) (MeO)2P(O)CH2COCH2OBn (12) was prepared as follows:
1) bromoacetic acid, KOH, BnOH, 140~200 °C, 2 d; 2) SOCl2
Article Identifier:
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Synlett 1999, No. 6, 692–694 ISSN 0936-5214 © Thieme Stuttgart · New York