S. Matsuda et al. / Tetrahedron Letters 48 (2007) 5807–5810
5809
12
J = 13.1 Hz, Hb-6), 4.19 (1H, t, J = 9.6 Hz, H-4), 4.59–
4.82 (4H, m, CH2Ph), 4.86 (1H, s, H-1), 5.16–5.23 (2H, m,
H-30), 5.27 (1H, dd, J = 3.4 Hz, J = 9.6 Hz, H-3), 5.81
(1H, m, H-20). 13C NMR (CDCl3, 150 MHz): d ꢀ5.4,
ꢀ5.2, 18.2, 25.8, 61.8, 67.9, 72.5, 73.1, 73.2, 75.2, 76.8,
using NaBH4 (8 equiv) at 0 °C for 3 h to successfully
afford the desired 2, which was purified by preparative
silica-gel TLC (hexane/ethyl acetate = 4/1) in 72% yield
as amorphous crystals. The NMR and mass spectra sup-
ported the formation of 2.13
1
88.3, 96.3, 117.8, 133.2. Compound 6: H NMR (CDCl3,
600 MHz): d 0.07 (3H, s, Si(CH3)2), 0.08 (3H, s, Si(CH3)2),
0.91 (9H, s, C(CH3)3), 2.01 (3H, s, CH3CO), 3.71 (1H, dd,
J = 1.4 Hz, J = 3.4 Hz, H-2), 3.80 (1H, dd, J = 5.5 Hz,
J = 11.0 Hz, Ha-6), 3.88 (1H, dd, J = 3.4 Hz, J = 8.9 Hz,
H-4), 3.85–3.93 (2H, m, Ha-10, Hb-6), 4.03 (1H, m, H-5),
4.23 (1H, m, Hb-10), 4.80 (1H, d, J = 1.4 Hz, H-1), 5.13
(1H, ddd, J = 1.4 Hz, J = 3.4 Hz, J = 10.3 Hz, Ha-30),
5.28 (1H, ddd, J = 1.4 Hz, J = 2.1 Hz, J = 18.6 Hz,
Hb-30), 5.33 (1H, t, J = 3.4 Hz, H-3), 5.87 (1H, m,
H-20). 13C NMR (CDCl3, 150 MHz): d ꢀ5.4 (Si(CH3)2),
ꢀ5.2 (Si(CH3)2), 18.2 (C(CH3)3), 21.0 (CH3CO), 25.8
(C(CH3)3), 62.7 (C-6), 67.3 (C-3), 67.4 (C-10), 68.9 (C-5),
70.7 (C-4), 71.5 (CH2Ph), 72.4 (CH2Ph), 75.6 (C-2), 97.5
(C-1, JC1–H1 = 164.7 Hz), 116.3 (C-30), 134.1 (C-20), 170.7
(CH3CO). HRMS (ESI): m/z calcd for C31H44O7SiÆNa+:
579.2749. Found: 579.2795. Compound 7: 1H NMR
(CDCl3, 600 MHz): d 0.05 (3H, s, Si(CH3)2), 0.08 (3H, s,
Si(CH3)2), 0.84 (9H, s, C(CH3)3), 3.61 (1H, dd, J = 1.4 Hz,
J = 3.8 Hz, H-2), 3.71 (1H, dd, J = 3.3 Hz, J = 9.5 Hz, H-
4), 3.76 (1H, dd, J = 5.7 Hz, J = 11.5 Hz, Ha-6), 3.83–3.85
(2H, m, H-5, Hb-6), 3.93 (1H, dtd, J = 1.2 Hz, J = 6.2 Hz,
J = 12.9 Hz, Ha-10), 4.04–4.06 (1H, m, H-3), 4.16 (1H,
dtd, J = 1.4 Hz, J = 5.3 Hz, J = 12.9 Hz, Hb-10), 4.82
(1H, d, J = 0.2 Hz, H-1), 5.11 (1H, ddd, J = 1.2 Hz,
J = 2.6 Hz, J = 10.3 Hz, Ha-30), 5.18 (1H, ddd,
J = 1.5 Hz, J = 3.1 Hz, J = 17.2 Hz, Hb-30), 5.81 (1H,
m, H-20). 13C NMR (CDCl3, 150 MHz): d ꢀ5.4, ꢀ5.2,
18.2, 25.9, 62.8, 66.6, 68.0, 68.2, 71.2, 71.9, 72.1, 76.6, 97.3
In summary, the partially benzylated anhydro-D-altro-
heptulose derivative 2 could be successfully synthesized
from the D-mannopyranoside derivative by a novel syn-
thetic approach involving the intramolecular O-glycosi-
dation developed by us. An investigation of the
preparation of several analogs of 2 by a similar synthetic
approach is now in progress.
References and notes
1. Hatano, T.; Yoshihara, R.; Hattori, S.; Yoshizaki, M.;
Shingu, T.; Okuda, T. Chem. Pharm. Bull. 1992, 40, 1703–
1710.
2. Dalmas, V.; Demuynck, C. Tetrahedron: Asymmetry 1993,
4, 1169–1172.
3. Hricoviniova-Bilikova, Z.; Petrus, L. Carbohydr. Res.
1999, 320, 31–36.
4. Francisco, C. G.; Herrera, A. J.; Suarez, E. J. Org. Chem.
2002, 67, 7439–7445.
5. (a) Yamanoi, T.; Oda, Y.; Matsuda, S.; Yamazaki, I.;
Matsumura, K.; Katsuraya, K.; Watanabe, M.; Inazu, T.
Tetrahedron 2006, 62, 10383–10392; (b) Yamanoi, T.;
Oda, Y.; Yamazaki, I.; Shinbara, M.; Morimoto, K.;
Matsuda, S. Lett. Org. Chem. 2005, 2, 242–246; (c)
Yamanoi, T.; Matsuda, S.; Yamazaki, I.; Inoue, R.;
Hamasaki, K.; Watanabe, M. Heterocycles 2006, 68, 673–
677; (d) Yamanoi, T.; Inoue, R.; Matsuda, S.; Katsuraya,
K.; Hamasaki, K. Tetrahedron: Asymmetry 2006, 17,
2914–2918.
6. Yamanoi, T.; Matsumura, K.; Matsuda, S.; Oda, Y.
Synlett 2005, 2973–2977.
7. Ogawa, T.; Nukada, T. Carbohydr. Res. 1985, 136, 135–
152.
8. Sato, K.; Yoshitomo, A. Chem. Lett. 1995, 39–40.
9. Ogawa, T.; Nakabayashi, S.; Kitajima, T. Carbohydr. Res.
1983, 114, 225–236.
10. Kuzuhara, H.; Fletcher, H. G. J. Org. Chem. 1967, 32,
2531–2534.
1
(C-1, JC1–H1 = 168.3 Hz), 117.9, 133.3. Compound 8: H
NMR (CDCl3, 600 MHz): d 0.04 (6H, s, Si(CH3)2), 0.89
(9H, s, C(CH3)3), 3.74–3.83 (5H, m, H-2, H-6, H-3, H-4 or
H-5), 3.98 (1H, dd, J = 6.2 Hz, J = 13.1 Hz, Ha-10), 4.09–
4.12 (2H, m, H-3, H-4 or H-5), 4.26 (1H, dd, J = 4.8 Hz,
J = 13.1 Hz, Hb-10), 4.83 (1H, d, J = 0.7 Hz, H-1), 5.15
(1H, dd, J = 1.4 Hz, J = 10.3 Hz, Ha-30), 5.29 (1H, dd,
J = 1.4 Hz, J = 19.2 Hz, Hb-30), 5.91 (1H, m, H-20). 13C
NMR (CDCl3, 150 MHz): d ꢀ5.4, ꢀ5.2, 18.3, 25.9, 63.0,
67.9, 70.2, 71.7, 72.0, 72.6, 72.8, 74.3, 76.5, 98.6 (C-1,
JC1–H1 = 167.5 Hz), 116.7, 134.4. Compound 9: b form:
1H NMR (CDCl3, 600 MHz): d 0.07 (3H, s, (SiCH3)2),
0.09 (3H, s, Si(CH3)2), 0.91 (9H, s, C(CH3)3), 3.47 (1H, t,
J = 2.1 Hz, H-2), 3.75 (1H, dd, J = 2.1 Hz, J = 2.8 Hz, H-
3), 3.85–3.90 (2H, m, H-4, Ha-6), 3.99–4.03 (2H, m H-5,
Hb-6), 4.33–4.77 (6H, m, CH2Ph), 5.06 (1H, d, J = 2.1 Hz,
H-1). 13C NMR (CDCl3, 150 MHz): d ꢀ5.4, ꢀ5.1, 18.3,
25.9, 62.6, 68.2, 71.7, 71.9, 72.4, 74.0, 75.5, 77.3, 92.8; a
form: 1H NMR (CDCl3, 600 MHz): d 0.07 (3H, s,
(CH3)2Si), 0.09 (3H, s, (CH3)2Si), 0.91 (9H, s, C(CH3)3),
3.53 (1H, dd, J = 2.1 Hz, J = 12.4 Hz, H-2), 3.59 (1H, d,
J = 4.1 Hz, H-4), 3.85–3.90 (2H, m, H-3 and Ha-6), 3.99–
4.03 (2H, m, H-5 and Hb-6), 4.33–4.68 (6H, m, CH2Ph),
5.04–5.08 (1H, m, H-1), 7.18–7.33 (15H, m Ph). 13C NMR
(CDCl3, 150 MHz): d ꢀ5.3, ꢀ5.0, 18.3, 25.9, 62.8, 68.2,
72.2, 73.065, 73.074, 73.5, 75.2, 77.3, 91.6. Compound 10:
1H NMR (CDCl3, 600 MHz): d 0.08 (3H, s, Si(CH3)2),
0.09 (3H, s, Si(CH3)2), 0.91 (9H, s, C(CH3)3), 3.86 (2H, d,
J = 3.2 Hz, H-6), 4.06 (1H, dd, J = 2.7 Hz, J = 6.3 Hz, H-
3), 4.23 (1H, dd, J = 2.7 Hz, J = 6.3 Hz, H-4), 4.26 (1H, d,
J = 6.3 Hz, H-2), 4.57–4.59 (1H, m, H-5), 4.47–4.94 (6H,
m, CH2Ph). 13C NMR (CDCl3, 150 MHz): d ꢀ5.4, ꢀ5.2,
18.3, 25.9, 62.0, 71.9, 72.6, 72.7, 73.6, 74.9, 75.7, 79.0,
168.7. Compound 11: 1H NMR (CDCl3, 600 MHz): d 0.08
(3H, s, Si(CH3)2), 0.09 (3H, s, Si(CH3)2), 0.91 (9H, s,
11. Imamoto, T.; Takiyama, N.; Nakamura, K.; Hatajima, T.;
Kamiya, Y. J. Am. Chem. Soc. 1989, 111, 4392–4398.
12. Nicotra, F.; Panza, L.; Russo, G. J. Org. Chem. 1987, 52,
5627–5630.
1
13. Spectroscopic data for 4: H NMR (CDCl3, 600 MHz): d
0.07 (3H, s, Si(CH3)2), 0.08 (3H, s, Si(CH3)2), 0.91 (9H, s,
C(CH3)3), 2.35 (1H, d, J = 9.6 Hz, OH), 3.57–3.60 (1H, m,
H-5), 3.65 (1H, t, J = 9.6 Hz, H-4), 3.74 (1H, dd,
J = 1.4 Hz, J = 3.4 Hz, H-2), 3.83–3.88 (2H, m, H-6),
3.92 (1H, dt, J = 4.1 Hz, J = 9.6 Hz, H-3), 3.93 (1H, dd,
J = 6.2 Hz, J = 13.1 Hz, Ha-10), 4.01 (1H, ddd, J =
1.4 Hz, J = 5.5 Hz, J = 13.1 Hz, Hb-10), 4.93 (1H, d,
J = 1.4 Hz, H-1), 5.16 (1H, dd, J = 1.4 Hz, J = 10.3 Hz,
Ha-30), 5.25 (1H, dd, J = 1.4 Hz, J = 17.2 Hz, Hb-30),
5.86 (1H, m, H-20). 13C NMR (CDCl3, 150 MHz): d ꢀ5.3,
ꢀ5.1, 18.3, 25.9, 62.6, 67.6, 71.8, 72.3, 72.7, 74.8, 76.6,
1
78.6, 95.7, 117.2, 133.8. Compound 5: H NMR (CDCl3,
600 MHz): d 0.069 (3H, s, (CH3)2Si), 0.073 (3H, s,
(CH3)2Si), 0.89 (9H, s, C(CH3)3), 3.62 (1H, dd,
J = 2.8 Hz, J = 12.4 Hz, H-5), 3.49 (1H, d, J = 11.7 Hz,
Ha-10), 3.88–3.93 (2H, m, Ha-6, Hb-10), 3.97 (1H, dd,
J = 2.1 Hz, J = 2.7 Hz, H-2), 4.10 (1H, dd, J = 5.5 Hz,