J. K. Gallos et al. / Tetrahedron Letters 42 (2001) 7489–7491
7491
gel, J. J. Chem. Soc., Perkin Trans. 1 2000, 3539–3554; (b)
Shin, K. L.; Moon, H. R.; George, C.; Marquez, V. E. J.
Org. Chem. 2000, 65, 2172–2178; (c) Moon, H. R.; Ford,
Jr., H.; Marquez, V. E. Org. Lett. 2000, 2, 3793–3796; (d)
Lee, K.; Cass, C.; Jacobsen, K. A. Org. Lett. 2001, 3,
597–599.
3. Gallos, J. K.; Koftis, T. V.; Koumbis, A. E. J. Chem. Soc.,
Figure 3.
Perkin Trans. 1 1994, 611–612.
4. (a) Gallos, J. K.; Dellios, C. C.; Spata, E. E. Eur. J. Org.
Chem. 2001, 79–82; (b) Hall, A.; Meldrum, K. P.;
Therond, P. R.; Wightman, R. H. Synlett 1997, 123–125;
(c) Thompson, D. K.; Hubert, C. N.; Wightman, R. H.
Tetrahedron 1993, 49, 3827–3840.
glycolic cleavage required prolonged stirring with an
excess of NaIO4 and yielded compound 12 upon
NaBH4 reduction, as a mixture with polyols 14 and 15
(Fig. 3), evidently because the initially formed hydroxy-
bis-aldehydes exist predominantly as lactols, resisting
the action of NaIO4. To overcome this problem, 11 was
subjected to two consecutive short-time glycolic cleav-
age/NaBH4 reduction treatments, to give the desired
compound 12, in good overall yield. Conventional ben-
zoylation of the two free hydroxyl groups and detrityla-
tion gave the known compound 13, which can be
readily converted to the nucleoside A-5021, according
to the literature procedure.9a
5. Doyle, M. P. Acc. Chem. Res. 1986, 19, 348–356.
6. The absolute configuration of the newly formed stereocen-
tre in 5 and 6 was deduced by NOE experiments. All new
compounds gave spectroscopic and analytical data consis-
tent with the proposed structures. NMR data for selected
1
compounds are listed. Compound 5: H NMR (CDCl3): l
0.66 (dd, 1 H, J=7.8, 5.9 Hz), 1.20 (dd, 1 H, J=5.9, 4.5
Hz), 1.30 (s, 3 H), 1.55 (s, 3 H), 1.6 (ddd, 1 H, J=7.8, 5.9,
4.0 Hz), 3.05 (br s, 2 H), 3.45 (d, 1 H, J=11.7 Hz), 3.79 (d,
1 H, J=11.7 Hz), 4.55 (dd as t, 1 H, J=6.8 Hz), 4.61 (d,
1 H, J=6.8 Hz), 4.88 (dd, 1 H, J=6.8, 4.0 Hz); 13C NMR
(CDCl3): l 10.9, 24.5, 26.1, 41.1, 65.1, 72.0, 79.2, 80.0,
In short, we have established preparative methods for
the directed intramolecular cyclopropanation of diazo
compound 2 to give bicyclo[3.1.0]hexane derivatives 3
or 4. Furthermore, we have demonstrated their syn-
thetic potential, by converting them into the sugar part
of cyclopentane, cyclopropane and bicyclo[3.1.0]hexane
nucleosides. Of particular interest is the synthesis of the
suger part of the antiviral cyclopropane nucleoside
A-5021, in enantiomerically pure form.
1
112.3. Compound 10: H NMR (CDCl3): l 1.33 (s, 3 H),
1.42 (s, 3 H), 2.27 (d 1 H, J=18.0 Hz), 2.67 (m, 1 H), 2.79
(dd, 1 H, J=18.0, 8.7 Hz), 2.91 (dd, 1 H, J=13.3, 6.3 Hz),
3.01 (dd, 1 H, J=13.3, 6.8 Hz), 4.32 (d, 1 H, J=5.0 Hz),
4.67 (d, 1 H, J=5.0 Hz), 7.3 (m, 5 H); 13C NMR (CDCl3):
l 24.8, 26.8, 37.0, 38.0, 39.5, 78.3, 81.1, 112.2, 127.0, 129.2,
130.3, 134.9, 212.9. Compound 12: 1H NMR (CDCl3): l
0.35 (dd as t, 1 H, J=5.4 Hz), 0.56 (dd, 1 H, J=8.3, 5.4
Hz), 1.30 (m, 1 H), 3.02 (d, 1 H, J=9.8 Hz), 3.19 (d, 1 H,
J=9.8 Hz), 3.28 (d, 1 H, J=11.7 Hz), 3.32 (dd, 1 H,
J=12.2, 5.4 Hz), 4.05 (dd, 1 H, J=12.2, 5.4 Hz), 4.15 (d,
1 H, J=11.7 Hz), 7.30 (m, 9 H), 7.45 (m, 6 H); 13C NMR
(CDCl3): l 13.7, 24.8, 26.7, 63.6, 65.7, 70.9, 87.0, 127.2,
128.0, 128.6, 143.6.
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