1192
H. R. Moon et al. / Tetrahedron: Asymmetry 13 (2002) 1189–1193
temperature for 1 h. After the mixture was allowed to
cool to 0°C, a solution of 3 (25.20 g, 132.5 mmol) in
THF (300 mL) was added and the mixture was stirred
at room temperature overnight. To this mixture was
carefully added water (200 mL) and the mixture was
extracted with ethyl acetate (4 L), dried, filtered and
evaporated under reduced pressure to give a yellow
syrup. This syrup was purified by silica gel column
chromatography using hexane and ethyl acetate (1:2–
1:2.5) as the eluent to give 8 (35 g) with the contamina-
tion of triphenylphosphine oxide, which was used for
next reaction without further purification: 1H NMR
(CDCl3), l ppm, J Hz: 1.35 (s, 3H, CH3), 1.45 (s, 3H,
CH3), 1.88 (br. s, 2H, 2*OH), 3.68–3.83 (m, 3H,
HOCH2CH(OH)-), 4.09 (dd, 1H, J=6.4, 8.4, 4-H), 4.69
(br. t, 1H, J=6.4, CH2ꢀCH-CH-), 5.32 (td, 1H, J=1.2,
10.4, CHHꢀCH-), 5.45 (td, 1H, J=1.6, 17.6,
CHHꢀCH-), 5.99 (ddd, 1H, J=6.8, 10.4, 17.6,
CH2ꢀCH-). Anal. calcd for C9H16O4: C, 57.43; H, 8.57.
Found: C, 57.54; H, 8.68%.
to 1b (13.88 g, 85%) according to the reported proce-
dure.6
Acknowledgements
This study was supported by a grant of the Korea
Health 21 R&D Project, Ministry of Health & Welfare,
Republic of Korea (01-PJ2-PG6-01NA01-0002).
References
1. Daluge, S. M.; Good, S. S.; Faletto, M. B.; Miller, W.
H.; St. Clair, M. H.; Boone, L. R.; Tisdale, M.; Parry, N.
R.; Reardon, J. E.; Dornsife, R. E.; Averett, D. R.;
Krenitsky, T. A. Antimicrob. Agents Chemother. 1997, 41,
1082–1093.
2. For a review about carbocyclic nucleosides, see: (a)
Borthwick, A. D.; Biggadike, K. Tetrahedron 1992, 48,
571–623; (b) Agrofoglio, L.; Suhas, E.; Farese, A.; Con-
dom, R.; Challand, S. R.; Earl, R. A.; Guedj, R. Tetra-
hedron 1994, 50, 10611–10670; (c) Marquez, V. E. Adv.
Antiviral Drug Design, 1996, 2, 89–146; (d) Crimmins, M.
T. Tetrahedron 1998, 54, 9229–9272.
3. (a) Coates, J. A.; Cammack, N.; Jenkinson, H. J.; Mut-
ton, I. M.; Pearson, B. A.; Storer, R.; Cameron, J. M.;
Penn, C. R. Antimicrob. Agents Chemother. 1992, 36,
202–205; (b) Schinazi, R. F.; Chu, C. K.; Peck, A.;
McMillan, A.; Mathis, R.; Cannon, D.; Jeong, L. S.;
Beach, J. W.; Choi, W.-B.; Yeola, S.; Liotta, D. C.
Antimicrob. Agents Chemother. 1992, 36, 672–676; (c)
Beach, J. W.; Jeong, L. S.; Alves, A. J.; Pohl, D.; Kim,
H. O.; Chang, C. N.; Doong, S. L.; Schinazi, R. F.;
Cheng, Y.-C.; Chu, C. K. J. Org. Chem. 1992, 57,
2217–2219; (d) Jeong, L. S.; Schinazi, R. F.; Beach, J. W.;
Kim, H. O.; Nampalli, S.; Shanmuganathan, K.; Alves,
A. J.; McMillan, A.; Chu, C. K. J. Med. Chem. 1993, 36,
181–195.
4. Parker, W. B.; Cheng, Y.-C. J. NIH Res. 1994, 6, 57–61.
5. (a) Chu, C. K.; Ma, T.; Shanmuganathan, K.; Wang, C.;
Xiang, Y.; Pai, S. B.; Tao, G.-Q.; Sommadossi, J.-P.;
Cheng, Y.-C. Antimicrob. Agents Chemother. 1995, 39,
979–981; (b) Lin, T.-S.; Luo, M.-Z.; Liu, M.-C.; Zhu,
Y.-L.; Gullen, E.; Dutschman, G. E.; Cheng, Y.-C. J.
Med. Chem. 1996, 39, 1757–1759.
4.8. (4S,5S)-2,2-Dimethyl-5-vinyl[1,3]dioxolane-4-car-
baldehyde, 910a,11
To a solution of crude 8 (35 g) in methylene chloride
(600 mL) was added aqueous NaIO4 (305.0 mL, 198.3
mmol, 0.65 M solution) at room temperature and the
reaction mixture was stirred at room temperature for 30
min. After methylene chloride (500 mL) and water (500
mL) were added, the organic layer was filtered, dried
and carefully evaporated under reduced pressure at
bellow 5°C until the volume of the mixture was approx.
30 mL. The solution was purified by short column silica
gel chromatography using diethyl ether as the eluent to
give 9 as a colorless oil (13.51 g, 65% from 3). Note:
ether should be evaporated carefully under a little
reduced pressure at bellow 5°C because of the volatility
1
of 9; H NMR (CDCl3), l ppm, J Hz: 1.42 (s, 3H,
CH3), 1.60 (s, 3H, CH3), 4.39 (dd, 1H, J=3.2, 7.2,
4-H), 4.83 (irregular t, 1H, J=6.8, 7.6, CH2ꢀCHCH-),
5.30 (td, 1H, J=1.2, 10.4, CHHꢀCH-), 5.44 (td, 1H,
J=1.2, 16.0, CHHꢀCH-), 5.73 (ddd, 1H, J=6.8, 10.4,
17.2, CH2ꢀCH-), 9.53 (d, 1H, J=3.2, C(O)H). Anal.
calcd for C8H12O3: C, 61.52; H, 7.74. Found: C, 61.55;
H, 7.59%; [h]2D5 +3.3 (c 1.33, CHCl3).
4.9. (1R,4R,5S)- and (1S,4R,5S)-1-(2,2-Dimethyl-5-
vinyl[1,3]dioxolan-4-yl)prop-2-en-1-ol, 10
6. Choi, W. J.; Park, J. G.; Yoo, S. J.; Kim, H. O.; Moon,
H. R.; Chun, M. W.; Jung, Y. H.; Jeong, L. S. J. Org.
Chem. 2001, 66, 6490–6494.
7. (a) Kiso, M.; Hasegawa, A. Carbohydr. Res. 1976, 52,
95–101; (b) Acevedo, O. L.; Townsend, L. B. In Nucleic
Acid Chemistry, Part Three: Improved and New Synthetic
Procedures, Methods and Techniques; Townsend, L. B.,
Compound 9 (26.49 g, 169.6 mmol) was converted to
10 (26.25 g, 84%) according to the reported procedure.6
4.10. (3aR,4R,6S)-2,2-Dimethyl-4,6a-dihydro-3aH-
cyclopenta[1,3]dioxol-4-ol, 11
Tipson, R. S., Eds. Synthesis of 2,3-O-isopropylidene-D-
Compound 10 (22.50 g, 122.1 mmol) was converted to
11 (a: 5.53 g, 29%, b: 11.34 g, 59%) according to the
reported procedure.6
ribose. John Wiley & Sons: New York, 1986; pp. 35–37;
(c) Ewing, D. F.; Humble, R. W.; Mackenzie, G.;
Raynor, A.; Shaw, G. Carbohydr. Res. 1991, 218, 233–
236; (d) Rauter, A. P.; Ramoa-Ribeiro, F.; Fernandes, A.
C.; Figueiredo, J. A. Tetrahedron 1995, 51, 6529–6540.
8. (a) Shing, T. K. M.; Elsley, D. A.; Gillhouley, J. G. J.
Chem. Soc., Chem. Commun. 1989, 1, 1280–1282; (b)
Redlich, H.; Sudau, W.; Szardenings, A. K.; Vollerthun,
4.11. (3aS,6aS)-2,2-Dimethyl-3a,6a-dihydrocy-
clopenta[1,3]dioxol-4-one, 1b
Compound 11 (16.47 g, 105.5 mmol) was converted