9776
A. Mart, M.S. Shashidhar / Tetrahedron 68 (2012) 9769e9776
13C NMR (CDCl3, 50.3 MHz):
d
137.9, 134.6, 134.0, 129.4, 128.4, 126.6,
Supplementary data
118.1, 117.5, 92.9, 81.3, 73.6, 73.5, 70.7, 69.9, 68.0 ppm.
1H and 13C NMR spectra for all new compounds. Supplementary
data associated with this article can be found in the online version,
4.4.3. 5-O-(4-Methoxy)benzyl-myo-inositol (46). Sodium hydride
(0.047 g, 1.20 mmol) was added to a cooled (0 ꢀC) solution of 45
(0.31 g, 0.80 mmol) in dry DMF (3 mL) and stirred for 15 min. PMBCl
(0.13 mL, 0.96 mmol) was added drop-wise to the stirred solution
and stirring continued for 2 h. The reaction mixture was worked up
using ethyl acetate. The gummy crude product obtained after the
evaporation of ethyl acetate was used for next step without
purification.
The crude product obtained above (0.25 g) and Pd(OH)2/C
(0.55 g) were refluxed in 2-propanol (3 mL) for 1.5 h. The reaction
mixture was filtered through a short bed of Celite and the Celite
washed with several portions of 1:1 mixture of water and metha-
nol. The combined washings were evaporated under reduced
pressure. Repeated washing of the residue with ethyl acetate
(3ꢂ5 mL) afforded the known 468(0.12 g, 78%) as a colorless solid.
References and notes
1. Lipshutz, B. H.; Pollart, D.; Monforte, J.; Kotsuki, H. Tetrahedron Lett. 1985, 26,
705e708.
2. (a) Toshima, K.; Yanagawa, K.; Mukaiyama, S.; Tatsuta, K. Tetrahedron Lett. 1990,
31, 6697e6698; (b) Wilson, N. S.; Keay, B. A. J. Org. Chem. 1996, 61, 2918e2919;
(c) Wilson, N. S.; Keay, B. A. Tetrahedron Lett. 1996, 37, 153e156; (d) Rotulo-Sims,
D.; Prunet, J. Org Lett. 2002, 4, 4701e4704.
3. (a) Boss, R.; Scheffold, R. Angew. Chem., Int. Ed. Engl. 1976, 15, 558e559; (b)
Smith, A. B., III; Rivero, R. A.; Hale, K. J.; Vaccaro, H. A. J. Am. Chem. Soc. 1991, 113,
2092e2112; (c) Mereyala, H. B.; Guntha, S. Tetrahedron Lett. 1993, 34,
6929e6930; (d) Vutukuri, D. R.; Bharathi, P.; Yu, Z.; Rajasekaran, K.; Tran, M.-H.;
Thayumanavan, S. J. Org. Chem. 2003, 68, 1146e1149.
4. (a) Jeffrey, P. D.; McCombie, S. W. J. Org. Chem. 1982, 47, 587e590; (b) Zhang, H.
X.; Guibe, F.; Balavoine, G. Tetrahedron Lett. 1988, 29, 623e626; (c) Lotz, B. T.;
Miller, M. J. J. Org. Chem. 1993, 58, 618e625.
4.4.4. Racemic 1,2-di-O-benzyl-3,4,5,6-tetra-O-methyl-myo-inositol
(49). Sodium hydride (1.25 g, 31.05 mmol) was added to a solution
of the diol 50 (1.65 g, 6.90 mmol) in dry DMF (20 mL) at 0 ꢀC and
stirred for 15 min. Benzyl bromide (3.3 mL, 27.6 mmol) was added
drop-wise to the reaction mixture and stirred for 4 h. After
quenching the excess sodium hydride by the addition of ice, the
solvents were evaporated under reduced pressure. The residue
obtained was worked up with ethyl acetate. The crude product was
purified by column chromatography (eluent: 25% ethyl acetate/
light petroleum) to afford 49 (2.50 g, 87%) as a colorless gum.
Found: C, 68.86; H, 7.94. C24H32O6 requires C, 69.21; H, 7.74%; Rf
(20% ethyl acetate/light petroleum) 0.31; 1H NMR (CDCl3,
5. (a) Sarin, G. S. Tetrahedron Lett. 1993, 34, 6309e6312; (b) Pal, M.; Parasuraman,
K.; Yeleswarapu, K. R. Org Lett. 2003, 5, 349e352.
6. Murali, C.; Shashidhar, M. S.; Gopinath, C. S. Tetrahedron 2007, 63,
4149e4155.
7. (a) Anthony, N. J.; Clarke, T.; Jones, A. B.; Ley, S. V. Tetrahedron Lett. 1987, 28,
5755e5758; (b) McKillop, A.; Taylor, R. J. K.; Watson, R. J.; Lewis, N. Synlett 1992,
1005e1006; (c) Schmeck, C.; Hegedus, L. S. J. Am. Chem. Soc. 1994, 116,
9927e9934.
8. Zhang, H.; Thompson, J.; Prestwich, G. D. Org Lett. 2009, 11, 1551e1554.
9. (a) Nicolaou, K. C.; Caulfield, T. J.; Kataoka, H.; Stylianides, N. A. J. Am. Chem. Soc.
1990, 112, 3693e3695; (b) Barili, P. L.; Berti, G.; Bertozzi, D.; Catelani, G.;
Colonna, F.; Corsetti, T.; D’Andrea, F. Tetrahedron 1990, 46, 5365e5376; (c)
Ziegler, F. E.; Brown, E. G.; Sobolov, S. B. J. Org. Chem. 1990, 55, 3691e3693; (d)
Ito, H.; Taguchi, T.; Hazawa, Y. J. Org. Chem. 1993, 58, 774e775; (e) Honda, M.;
Morita, H.; Nagakura, I. J. Org. Chem. 1997, 62, 8932e8936.
10. Oikawa, Y.; Yoshioka, T.; Yonemitsu, O. Tetrahedron Lett. 1982, 23, 885e888.
11. Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722e9723.
12. Bennett, M.; Onnebo, S. M.; Azevedo, C.; Saiardi, A. Cell. Mol. Life. Sci. 2006, 63,
552e564.
13. Illies, C.; Gromada, J.; Fiume, R.; Leibiger, B.; Yu, J.; Juhl, K.; Yang, S.-N.; Barma,
D. K.; Falck, J. R.; Saiardi, A.; Barker, C. J.; Berggren, P.-O. Science 2007, 318,
1299e1302.
14. Saiardi, A.; Resnick, A. C.; Snowman, A. M.; Wendland, B.; Snyder, S. H. Proc.
Natl. Acad. Sci. USA 2005, 102, 1911e1914.
200 MHz):
d
7.22e7.43 (m, 10H, ArH), 4.83 (q, 2H, J¼12.1 Hz, OCH2),
4.64 (q, 2H, J¼11.9 Hz, OCH2), 4.01 (t, 1H, J¼2.3 Hz, InsH), 3.50e3.70
(m, 11H, 3ꢂOCH3, 2InsH), 3.37 (s, 3H, OCH3), 3.20 (dd, 1H, J¼9.9,
2.4 Hz, InsH), 2.88e3.04 (m, 2H, InsH) ppm; 13C NMR (CDCl3,
50.3 MHz):
d 138.9, 138.5, 128.3, 128.0, 127.6, 127.5, 127.3, 127.2,
85.6, 83.3, 82.9, 82.4, 80.6, 73.8, 73.3, 72.8, 61.1, 60.8, 58.2 ppm.
15. York, S. J.; Armbruster, B. N.; Greenwell, P.; Petes, T. D.; York, J. D. J. Biol. Chem.
2005, 280, 4264e4269.
16. Saiardi, A.; Bhandari, R.; Resnick, A. C.; Snowman, A. M.; Snyder, S. H. Science
4.4.5. Reaction of 49 with Pd(OH)2/C in 2-propanol. A mixture of 49
(1.0 g, 2.40 mmol) and Pd(OH)2/C (20 wt %, 2.20 g) was refluxed in
2-propanol for 60 h. The reaction mixture was filtered through
a short bed of Celite and the Celite washed with methanol followed
by ethyl acetate. The combined washings were evaporated under
reduced pressure and the residue was purified by column chro-
matography (eluent: 50% ethyl acetate in light petroleum) to afford
51 (0.18 g, 23%) as a colorless oil and 5035 (eluent: 15% methanol/
ethyl acetate) as a colorless solid (0.41 g, 74%); mp¼97e99.3 ꢀC
(lit.35 mp 105e106 ꢀC). Data for 51: Found: C, 60.30; H, 7.54.
C17H24O7 requires C, 59.99; H, 7.11%; Rf (40% ethyl acetate/light
2004, 306, 2101e2105.
17. (a) King, J. F.; Allbutt, A. D. Can. J. Chem. 1970, 48, 1754e1769; (b) Godage, H.
Y.; Riley, A. M.; Woodman, T. J.; Potter, B. V. L. Chem. Commun. 2006,
2989e2991.
18. del Carmen Cruzado, M.; Martin-Lomas, M. Tetrahedron Lett. 1986, 27,
2497e2500.
19. Smidt, J.; Hafner, W.; Jira, R.; Sedlmeier, J.; Sieber, R.; Ruttinger, R.; Kojer, H.
Angew. Chem. 1959, 71, 176e182.
20. Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory Chemicals, 2nd ed.;
Pergamon: Oxford, UK, 1988.
21. Micali, E.; Chehade, K. A. H.; Isaacs, R. J.; Andres, D. A.; Spielmann, H. P. Bio-
chemistry 2001, 40, 12254e12265.
petroleum); IR (CHCl3):
200 MHz): 8.03e8.09 (m, 2H, ArH), 7.55e7.61 (m, 1H, ArH),
n
3120e3660, 1724 cmꢁ1 1H NMR (CDCl3,
;
22. Saburi, H.; Tanaka, S.; Kitamura, M. Angew. Chem., Int. Ed. 2005, 44, 1730e1732.
23. Enholm, E.; Low, T. J. Org. Chem. 2006, 71, 2272e2276.
24. Berry, J. M.; Hall, L. D. Carbohydr. Res. 1976, 47, 307e310.
25. Nayak, S. K.; Kadam, S. M.; Banerji, A. Synlett 1993, 581e582.
26. Fuwa, H.; Yamaguchi, H.; Sasaki, M. Org. Lett. 2010, 12, 1848e1851.
27. Hernandez, A.; Familiar, O.; Negri, A.; Rodriguez-barrios, F.; Gao, F.; Karlsson,
A.; Camarasa, M.; Balzarini, J.; Perez-perez, M. J. Med. Chem. 2006, 49,
7766e7773.
28. Pollard, M. M.; ter Wiel, M. K. J.; van Delden, R. A.; Vicario, J.; Koumura, N.;
van den Brom, C.; Meetsma, A.; Feringa, B. L. Chem.e Eur. J. 2008, 14,
11610e11622.
29. Otera, J.; Dan-oh, N.; Nozaki, H. Tetrahedron 1993, 49, 3065e3074.
30. Sharghi, H.; Sarvari, M. H. Tetrahedron 2003, 59, 3627e3633.
31. Anderson, R. C.; Wallis, E. S. J. Am. Chem. Soc. 1948, 70, 2931e2935.
32. Devaraj, S.; Shashidhar, M. S.; Dixit, S. S. Tetrahedron 2005, 61, 529e536.
33. The MERCK INDEX. 11th ed.; Merck: NJ, USA, 1989, p 170.
34. Kostas, I. D. J. Organomet. Chem. 2001, 634, 90e98.
d
7.43e7.51 (m, 2H, ArH), 5.89 (t, 1H, J¼2.8 Hz, InsH), 3.69 (s, 3H,
OCH3), 3.67 (s, 3H, OCH3), 3.61e3.65 (m, 4H, OCH3, InsH), 3.49e3.60
(m, 3H, InsH), 3.45 (s, 3H, OCH3), 3.09e3.26 (m, 2H, InsH, OH) ppm;
13C NMR (CDCl3, 50.3 MHz):
d 166.0, 133.1, 130.0, 129.9, 128.4, 85.3,
83.7, 83.3, 80.5, 70.2, 69.5, 61.2, 61.1, 61.0, 58.0 ppm.
Acknowledgements
A.M. is a recipient of a Senior Research Fellowship (SRF) from the
Council of Scientific and Industrial Research (CSIR), New Delhi. We
appreciate receiving a research grant from the Director, National
Chemical Laboratory.
35. Dixit, S. S.; Shashidhar, M. S. Tetrahedron 2008, 64, 2160e2171.