4154
C. Murali et al. / Tetrahedron 63 (2007) 4149–4155
1.03 mmol) and 20% Pd(OH)2/C (0.359 g) were refluxed in
methanol (5 mmol) for 10 h under argon atmosphere. The
reaction mixture was allowed to cool to room temperature
and the catalyst was filtered using a short bed of Celite.
The catalyst was washed with methanol (2ꢂ5 mL). The
crude product obtained was purified by column chromato-
graphy (10% ethyl acetate in petroleum ether) to get cyclo-
hexanol (17) as a colourless liquid (0.086 g, 84%).
A mixture of the methyl ether of 18 (0.280 g, 0.53 mmol) ob-
tained above and 20% Pd(OH)2/C (0.554 g) in methanol
(5 mL) was refluxed under argon atmosphere for 20 h. The
reaction mixture was allowed to cool to rt and diluted with
3 mL of water. The catalyst was filtered using a short bed
of Celite and was washed with water (2ꢂ3 mL). The crude
product obtained by evaporation of the filtrate, was dissolved
in methanol and water mixture (3:1) and cooled in a freezer
to get colourless crystals of 19 (0.096 g, 94%). Mp 237–
239 ꢀC (lit.31 mp 238–239 ꢀC).
4.1.15. Reaction of cyclohexyl benzyl ether (16) with
Pd(OAc)2 in methanol. A mixture of the benzyl ether 16
(0.048 g, 0.25 mmol) and Pd(OAc)2 (0.028 g, 0.13 mmol)
in methanol (5 mL) was refluxed for 40 h under argon atmo-
sphere. The product, cyclohexanol (17, 0.021 g, 83%) was
isolated as above.
Acknowledgements
This work was supported by the Department of Science and
Technology, New Delhi, in the form of a research grant to
M.S.S. C.M. thanks Council of Scientific and Industrial
Research, New Delhi, for Senior Research Fellowship.
4.1.16. Reduction of 2,4,6-tri-O-benzyl-myo-inositol
1,3,5-orthobenzoate (8) with DIBAL-H.21 Solution of
DIBAL-H (1 M) in toluene (4 mL, 4.0 mmol) was added
drop wise over a period of 15 min to a solution of 8 (1.073 g,
2.0 mmol) in dry dichloromethane (16 mL) at 0 ꢀC and
stirred at rt for 2 h. The reaction mixture was poured into
a stirred solution of saturated Na/K tartrate (10 mL) and
ammonium chloride (10 mL) and stirred for 2 h. The
mixture was extracted with ethyl acetate (2ꢂ100 mL) and
usual workup followed by column chromatography (ethyl
acetate:dichloromethane:petroleumether¼1:1:8) afforded
18 as a solid (1.05 g, 97%). Mp 102–104 ꢀC (crystallized
from a solution of dichloromethane and light petroleum
References and notes
1. (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; Wiley: New York, NY, 1999; (b) Jarowicki,
K.; Kocienski, P. J. Chem. Soc., Perkin Trans. 1 2001, 2109; (c)
Kocienski, P. J. Protecting Groups, 3rd ed.; Georg Thieme:
Stuttgart, Germany and New York, NY, 2005.
2. Lipshutz, B. H.; Pollart, D.; Monforte, J.; Kotsuki, H.
Tetrahedron Lett. 1985, 26, 705.
3. Anthony, N. J.; Clarke, T.; Jones, A. B.; Ley, S. V. Tetrahedron
Lett. 1987, 28, 5755.
4. McKillop, A.; Taylor, R. J. K.; Watson, R. J.; Lewis, N. Synlett
1992, 1005.
5. Schmeck, C.; Hegedus, L. S. J. Am. Chem. Soc. 1994,
116, 9927.
6. Haribabu, M.; Sreenivasulu, G. Tetrahedron Lett. 1993,
34, 6929.
7. (a) Wilson, N. S.; Keay, B. A. J. Org. Chem. 1996, 61, 2918; (b)
Wilson, N. S.; Keay, B. A. Tetrahedron Lett. 1996, 37, 153; (c)
Hattori, K.; Sajiki, H.; Hirota, K. Tetrahedron 2000, 56, 8433;
(d) Hattori, K.; Sajiki, H.; Hirota, K. Tetrahedron Lett. 2000,
41, 5711; (e) Hattori, K.; Sajiki, H.; Hirota, K. Tetrahedron
2001, 57, 2109; (f) Ikawa, T.; Sajiki, H.; Hirota, K.
Tetrahedron 2004, 60, 6189; (g) Ikawa, T.; Hattori, K.; Sajiki,
H.; Hirota, K. Tetrahedron 2004, 60, 6901.
1
ether cooled to 0 ꢀC), IR (neat) y¼3452 (OH) cmꢁ1; H
NMR (CDCl3, 200 MHz): d 7.50–7.60 (m, 2H, Ar H),
7.27–7.45 (m, 18H, Ar H), 5.72 (s, 1H, PhCH), 4.58–4.81
(m, 6H, CH2), 4.41 (d, 2H, J¼2 Hz, Ins H), 3.96–4.15 (m,
2H, Ins H), 3.79 (t, 1H, J¼8.64 Hz, Ins H), 3.62 (t, 1H,
J¼2.44 Hz, Ins H), 2.57 (s, 1H, OH). 13C NMR (CDCl3,
50.3 MHz): d 137.9 (Cipso), 137.8 (Cipso), 137.3 (Cipso),
129.3 (Carom), 128.4 (Carom), 128.3 (Carom), 128.2 (Carom),
127.9 (Carom), 127.8 (Carom), 127.6 (Carom), 126.5 (Carom),
92.7 (PhCH), 81.5 (Ins C), 73.5 (Ins C), 73.4 (Ins C), 71.6
(CH2), 70.6 (CH2), 68.1 (Ins C). Anal. calcd for C34H34O6:
C, 75.82; H, 6.36. Found: C, 75.80; H, 6.40.
4.1.17. Preparation of sequoyitol (19). Sodium hydride
(0.040 g, 0.10 mmol) was added to a solution of 18
(0.480 g, 0.89 mmol) in dry DMF (3 mL) and stirred for
30 min. The mixture was cooled to 0 ꢀC and methyl iodide
(0.182 g, 1.28 mmol) was added drop wise and the mixture
stirred for 1 h at rt. The reaction mixture was concentrated
under reduced pressure and worked up with chloroform.
Column chromatography (10% ethyl acetate in petroleum
ether) of the residue obtained after evaporation of chloro-
form afforded the methyl ether of 18 as a solid (0.481 g,
98%). Mp¼85–88 ꢀC, 1H NMR (CDCl3, 200 MHz):
d 7.50–7.55 (m, 2H, Ar H), 7.25–7.45 (m, 18H, Ar H),
5.74 (s, 1H, PhCH), 4.56–4.76 (m, 6H, CH2), 4.37 (d, 2H,
J¼2 Hz, Ins H), 4.02 (d, 2H, J¼7 Hz, Ins H), 3.56–3.63
(m, 1H, Ins H), 3.59 (s, 3H, OCH3), 3.44 (t, 1H, J¼7 Hz,
Ins H). 13C NMR (CDCl3, 50.3 MHz): d 138.0 (Cipso),
137.8 (Cipso), 137.5 (Cipso), 129.2 (Carom), 128.3 (Carom),
128.2 (Carom), 127.7 (Carom), 127.6 (Carom), 126.4 (Carom),
92.8 (PhCH), 83.5 (Ins C), 82.3 (Ins C), 73.2 (Ins C), 71.4
(CH2), 70.6 (CH2), 68.2 (Ins C), 59.7 (OCH3). Anal. calcd
for C35H36O6: C, 76.06; H, 6.56. Found: C, 76.21; H, 6.43.
ꢀ
8. (a) Zhang, H. X.; Guibe, F.; Balavoine, G. Tetrahedron Lett.
1998, 29, 623; (b) Genet, J. P.; Blart, E.; Savignac, M.;
ꢀ
Lemeune, S.; Lemaire-Audoire, S.; Paris, J. M.; Bernard,
J. M. Tetrahedron 1994, 50, 497.
9. Mino, T.; Hirota, T.; Yamashita, M. Synlett 1996, 999.
10. Jungheim, L. N. Tetrahedron Lett. 1989, 30, 1889.
11. (a) Billington, D. C. The Inositol Phosphates. Chemical
Synthesis and Biological Significance; VCH: New York, NY,
1993; (b) Chida, N.; Koizumi, K.; Kitada, Y.; Yokoyama, C.;
Ogawa, S. J. Chem. Soc., Chem. Commun. 1994, 111; (c)
Potter, B. V. L.; Lampe, D. Angew. Chem., Int. Ed. Engl. 1995,
34, 1933; (d) Phosphoinositides: Chemistry, Biochemistry and
Biomedical Applications; Bruzik, K. S., Ed.; ACS Symposium
Series 718; American Chemical Society: Washington DC,
1999; (e) Sureshan, K. M.; Shashidhar, M. S.; Praveen, T.;
Das, T. Chem. Rev. 2003, 103, 4477.
12. (a) Sarmah, M. P.; Shashidhar, M. S.; Sureshan, K. M.;
Gonnade, R. G.; Bhadbhade, M. M. Tetrahedron 2005, 61,