H. Abe et al. / Tetrahedron Letters 42 (2001) 6159–6161
6161
Acknowledgements
Fuchs, P. L. Synth. Commun. 1986, 16, 111–115) resulted
in many spots on TLC.
We are grateful to the Japan Society for Promotion of
Science for Grant-in-Aid for Creative Scientific
Research (13NP0401) and also for support of H.A.
8. Successive treatment of 1 with BuLi (3.5 equiv.) and
TIPSOTf (4.0 equiv.) in THF produced the desired fully
silylated 3 in only 10% yield.
9. Physical data of the typical products are as follows. 3
(oil): 1H NMR (CDCl3, 400 MHz) l 7.58–7.24 (m, 5H,
Ar), 5.66 (s, 1H, H-1), 4.58 (d, 1H, H-5a, J=12.3 Hz),
4.20 (s, 1H, H-3), 3.99 (s, 1H, H-2), 3.75 (s, 1H, H-4),
3.19 (d, 1H, H-5b, J=12.3 Hz), 1.08 (m, 63H, TIPS×3);
HRMS (ESI) calcd for C38H74O4SeSi3Na 781.3957
(MNa+), found 781.3984. Anal. calcd for C38H74O4SeSi3:
References
1. (a) Lalonde, M.; Chan, T. H. Synthesis 1985, 817–845;
(b) Ru¨cker, C. Chem. Rev. 1995, 95, 1009–1064; (c)
Nelson, T. D.; Crouch, R. D. Synthesis 1996, 1031–1069.
2. (a) Hosoya, T.; Ohashi, Y.; Matsumoto, T.; Suzuki, K.
Tetrahedron Lett. 1996, 37, 663–666; (b) Futagami, S.;
Ohashi, Y.; Imura, K.; Hosoya, T.; Ohmori, K.; Mat-
sumoto, T.; Suzuki, K. Tetrahedron Lett. 2000, 41, 1063–
1067.
3. X-Ray crystallographic analysis of a 3,4,6-tris-O-TBS-
glucose derivative in a 1C4-conformation: Walford, C.;
Jackson, R. F. W.; Rees, N. H.; Clegg, W.; Heath, S. L.
Chem. Commun. 1997, 1855–1856.
1
C, 60.20; H, 9.84. Found: C, 59.92; H, 9.59. 7 (oil): H
NMR (CDCl3, 500 MHz) l 7.62–7.21 (m, 5H, Ar), 5.47
(d, 1H, H-1, J=2.9 Hz), 4.31 (br s, 1H, H-2), 4.25 (dd,
1H, H-6a, J=6.0, 9.9 Hz), 4.14 (br s, 1H, H-3), 4.04 (br
s, 1H, H-4), 4.02 (m, 2H, H-5, H-6b). 1.06 (m, 84H,
TIPS×4); HRMS (ESI) calcd for C48H96O5SeSi4Na
967.5397 (MNa+), found 967.5389. Anal. Calcd for
C48H96O5SeSi4·H2O: C, 59.89; H, 10.26. Found: C, 59.57;
1
H, 10.20. 16 (oil): H NMR (CDCl3, 400 MHz) l 6.56 (d,
4. Ichikawa, S.; Shuto, S.; Matsuda, A. J. Am. Chem. Soc.
1H, NH, J=9.9 Hz), 4.84 (d, 1H, H-1, J=1.8 Hz), 4.28
(ddd, 1H, H-2, J=1.8, 3.0, 9.9 Hz), 4.14 (m, 2H, H-6×2),
4.08 (dd, 1H, H-3, J=2.0, 3.0 Hz), 3.94 (dd, 1H, H-5,
J=8.5, 11.4 Hz), 3.81 (d, 1H, H-4, J=2.0 Hz), 3.49 (s,
3H, OMe), 1.96 (s, 3H, OAc), 1.09–1.05 (m, 63H, TIPS×
3); MS (ESI) m/z 727 (MNa+). Anal. calcd for
C36H77NO6Si3: C, 61.40; H, 11.02; N, 1.99. Found C,
61.33; H, 11.04; N, 1.80. The small J2,3 and J3,4 values of
these silylated pyranosides in their 1H NMR spectra
showed that their conformations were restricted to the
1999, 121, 10270–10280.
5. (a) Yahiro, Y.; Ichikawa, S.; Shuto, S.; Matsuda, A.
Tetrahedron Lett. 1999, 40, 5527–5531; (b) Shuto, S.;
Yahiro, Y.; Ichikawa, S.; Matsuda, A. J. Org. Chem.
2000, 65, 5547–5557; (c) Shuto, S.; Terauchi, M.; Yahiro,
Y.; Abe, H.; Ichikawa, S.; Matsuda, A. Tetrahedron Lett.
2000, 41, 4151–4155.
6. When
1 was treated with TIPSOTf/2,6-lutidine in
CH2Cl2, well known efficient conditions for the introduc-
tion of a bulky silyl group at sterically hindered hydroxy-
ls (Corey, E. J.; Cho, H.; Rucker, C.; Hua, D. H.
Tetrahedron Lett. 1981, 22, 3455–3458) the corresponding
2,4-bis-O-TIPS product was obtained in 89% yield.
1
unusual C4-form.
10. When methyl a-
D-mannoside was used as a substrate in
this reaction, none of the desired fully silylated product
was obtained, where methyl 2,4,6-tris-O-TIPS-a-D-man-
noside was obtained in 68% yield.
11. For example see: Preparative Carbohydrate Chemistry;
7. Treatment of 1 with KH and TIPSCl in the presence of
18-crown-6 in THF, which was reported to be effective in
silylating extremely hindered alcohols (Braish, T. F.;
Hanessian, S., Eds.; Marcel Dekker: New York, 1997.
.