6.0 Hz), 2.16–2.28 (2H, m), 1.88–1.93 (2H, m), 1.62–1.66 (1H, m),
1.48–1.55 (1H, m), 1.37–1.44 (1H, m), 1.21–1.29 (1H, dd, J =
24.0, 12.0 Hz) ppm. 13C NMR (100 MHz): d 174.3, 72.4, 67.9,
56.2, 54.9, 49.7, 39.5, 32.1, 28.5, 17.6 ppm. MS/ESI : [M + H]+
Calcd;216.1236; found: 216.1235.
625; (d) N. Asano, Curr. Top. Med. Chem., 2003, 3, 471; (e) T. D. Butters,
R. A. Dwek and F. M. Platt, Chem. Rev., 2000, 100, 4683.
2 Selected publications on the construction of bicyclic azasugars: (a) M.
Pourashraf, P. Delair, M. O. Rasmussen and A. E. Greene, J. Org.
Chem., 2000, 65, 6966; (b) H. Zhao, S. Hans, X. Cheng and D. R.
Mootoo, J. Org. Chem., 2001, 66, 1761; (c) W. H. Pearson and E. J.
Hembre, Tetrahedron Lett, 2001, 42, 8273; (d) J. -B. Behr, A. Erard and
G. Guillerm, Eur. J. Org. Chem., 2002, 1256; (e) J. A. Vanecko and F. G.
West, Org. Lett., 2002, 4, 2813; (f) W. H. Pearson, L. Guo and T. M.
Jewell, Tetrahedron Lett., 2002, 43, 2175; (g) F. Cardona, E. Faggi, F.
Liguori, M. Cacciarini and A. Goti, Tetrahedron Lett., 2003, 44, 2315.
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Phytomedicine, 2007, 14, 353; (b) P. E. Goss, C. L. Reid, D. Bailey and
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Lagana, J. G. Goetz, I. R. Nabi, P. Cheung, A. Raz and J. W. Dennis,
Mol. Cell Biol., 2006, 26, 3181.
(2R,3R,4S,9aS)-4-(Acetoxymethyl)-6-oxooctahydro-1H-quino-
lizine-2,3-diyl diacetate (27a). The same experimental procedure
for the synthesis of 25a from 9 was followed. Yield: 98% (92 mg,
25
viscous liquid). Rf: 0.50 (ethyl acetate). [a]D = -13 (c 1.1,
CH2Cl2). IR nmax: 1670, 3400 cm-1. 1H NMR (500 MHz, CDCl3):
d 5.45–5.47 (1H, m), 5.40–5.43 (1H, m), 4.23 (1H, d, J = 8.0 Hz),
4.29–4.32 (1H, dd, J = 6.3, 4.45 Hz), 3.79–3.85 (1H, m), 2.42–2.48
(1H, m), 2.31–2.38 (1H, m), 2.07 (3H, s, OAc), 2.06 (3H, s, OAc),
2.03 (3H, s, OAc), 1.74–1.96 (2H, m), 1.36–1.43 (1H, m) ppm. 13
C
4 P. V. Murphy and L. Cronin, Org. Lett., 2005, 7, 2691.
5 (a) M. S. J. Simmonds, W. M. Blaney and L. E. Fellows, J. Chem.
Ecol., 1990, 16, 3167; (b) D. J. Robins, Nat. Prod. Rep., 1990, 7,
377; (c) R. J. Nash, L. E. Fellows, J. V. Dring, G. W. J. Fleet, A.
Girdhar, N. G. Ramsden, J. V. Peach, M. P. Hegarty and A. M. Scofield,
Phytochemistry, 1990, 29, 114.
NMR (125.7 MHz): d 171.0, 170.4, 169.7, 169.5, 67.7, 64.6, 62.0,
53.7, 51.7, 35.9, 32.6, 30.0, 20.8, 20.7, 19.7 ppm. MS/ESI : [M +
H]+ Calcd; 342.1553; found: 342.1551.
(2R,3R,6S ,7R,8R,9aR)-7,8-Bis(benzyloxy)-6-(benzyloxy-
methyl)-4-oxooctahydro-1H-quinolizine-2,3-diyl diacetate (29).
The same experimental procedure for the synthesis of 25a from
9 was followed. Yield: 99% (99 mg, viscous liquid). Rf: 0.50 (1:1
6 (a) H. Hamana, N. Ikota and B. Ganem, J. Org. Chem., 1987, 52,
5492; (b) G. Rassu, G. Casiraghi, L. Pinna, P. Spanu, F. Ulgheri, M.
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Berger, V. Grassberger, A. E. Stu¨tz and G. Legler, Tetrahedron Lett,
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F. Sztaricskai, A. Berecibar, C. Riche, A. Chiaroni, A. Olesker and G.
Lukacs, Tetrahedron, 1995, 51, 2969; (h) H. S. Overkleeft, P. Bruggeman
and U. K. Pandit, Tetrahedron Lett., 1998, 39, 3869; (i) P. S. Liu, R. S.
Rogers, M. S. Kang and P. S. Sunkara, Tetrahedron Lett., 1991, 32,
5853; (j) P. S. Liu, J. Org. Chem., 1987, 52, 4717; (k) C. Schaller and
P. Vogel, Hel. Chim. Acta., 2000, 83, 193; (l) K. S. Ajish Kumar, V. D.
Chaudhari and D. D. Dhavale, Org. Biomol. Chem., 2008, 6, 703; (m) P.
Gebarowsky and W. Sas, Chem. Commun., 2001, 915; (n) H. L. Verhelst,
B. P. Martinez, M. S. M. Timmer, G. Lodder, G. A. van der Marel, H. S.
Overkleeft and J. H. van Boom, J. Org. Chem., 2003, 68, 9598; (o) G.
Lesma, Tetrahedron Asymmetry, 2007, 18, 1948.
7 (a) R. V. Doddi, H. P. Kokatla, A. P. John Pal, R. K. Basak and Y. D.
Vankar, Eur. J. Org. Chem., 2008, 34, 5731; (b) Mohammad A. Alam,
A. Kumar and Y. D. Vankar, Eur. J. Org. Chem., 2008, 29, 4972; (c) A.
Kumar, G. K. Rawal and Y. D. Vankar, Tetrahedron, 2008, 64, 2379;
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(e) K. Jayakanthan and Y. D. Vankar, Tetrahedron Lett., 2006, 47, 8667;
(f) K. Jayakanthan and Y. D. Vankar, Org. Lett., 2005, 7, 5441; (g) G. B.
Reddy and Y. D. Vankar, Angew. Chem. Int. Ed., 2005, 44, 2001; (h) S.
Rani, A. Agarwal and Y. D. Vankar, Tetrahedron Lett., 2003, 44, 5001.
8 G. K. Rawal, A. Kumar, U. Tawar and Y. D. Vankar, Org. Lett., 2007,
9, 5171.
25
hexane–ethyl acetate). [a]D = -40 (c 1.0, CH2Cl2). IR nmax: 1670,
1
3400 cm-1. H NMR (500 MHz, CDCl3): d 5.40 (1H, br.s, H-7),
5.36 (1H, br.s, H-8), 5.03 (1H, br.d J = 3.0 Hz, H-4), 4.7–4.76
(3H, m, -OCH2Ph), 4.66 (1H, d, J = 11.5 Hz, -OCH2Ph), 4.50
(1H, d, J = 12.0 Hz, -OCH2Ph) 4.43 (1H, d, J = 11.5 Hz,
-OCH2Ph), 3.97–4.12 (3H, m, H-10, H-10, H-2), 3.79–3.82 (1H,
br.t, J = 4.5 Hz, H-11¢), 3.57–3.60 (1H, t, J = 8.5 Hz, H-3), 2.25–
2.28 (1H, m, H-9) 2.17 (3H, s, OAc), 2.04–2.08 (1H, m, H-1), 1.86
(3H, s, OAc), 1.69–1.74 (1H, m, H-9¢), 1.24–1.41 (1H, m, H-1¢)
ppm. 13C NMR (125.7 MHz): d 170.1, 165.4, 138.7, 138.3, 128.4,
128.3, 127.6, 127.5, 127.4, 127.3, 80.4, 75.7, 73.4, 72.6, 68.8, 68.4,
67.6, 51.5, 48.7, 38.5, 32.4, 20.7 ppm. MS/ESI : [M + H]+ Calcd;
602.2754; found: 602.2752.
Acknowledgements
We thank the Department of Science and Technology (DST), New
Delhi, for financial support to Y.D.V. in the form of a Ramanna
Fellowship (Grant No. SR/S1/RFOC-04/2006). N.K. thanks the
University Grant Commission, New Delhi, for a Senior Research
Fellowship.
9 N. Kumari, B. G. Reddy and Y. D. Vankar, Eur. J. Org. Chem., 2009, 1,
160.
10 (a) M. Kawana, Chem. Lett., 1981, 1541; (b) K. Hirota, Y. Monguchi,
Y. Kitade and H. Sajiki, Tetrahedron, 1997, 53, 16683.
11 T. L. Suyama and W. H. Gerwick, Org. Lett., 2006, 8, 4541.
12 Y.-T. Li and S.-C. Li, Methods in Enzymology, ed. V. Ginsberg,
Academic Press, 1972, p. 702.
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