K. Vanlaldinpuia, G. Bez / Tetrahedron Letters 52 (2011) 3759–3764
3763
Table 3 (continued)
Entry
Substrate
Product
Time (h)
Isolated yield (%)b
Ref. (reported yield %)
O
O
O
O
O
O
O
13
2d
83
27 (79)
O
O
O
HO
HO
O
OH
13b
O
O
O
O
14
2
93
24a (91)
O
O
O
HO
14b
a
b
c
Typical reaction conditions: substrate (1 mmol), acetonitrile/water (2 mL, 9:1 v/v), PTA (5 mol %), room temperature unless otherwise stated.
The products were characterized by 1H NMR, 13C NMR, Mass and IR spectroscopy and compared with the literature data.
Complete hydrolysis led to generation of
10 mol % catalyst was used.
D-galactose.
d
e
Confirmed by comparing with commercially available authentic sample.
7. Silvana, P.; Annalisa, G.; Daniele, D.; Mauro, D. N.; Giovanni, P. Synthesis 2006,
305.
8. Khan, A. T.; Khan, M. M. Carbohydr. Res. 2010, 345, 154.
9. Lin, C.-C.; Jan, M.-D.; Weng, S.-S.; Lin, C.-C.; Chen, C.-T. Carbohydr. Res. 2006,
341, 1948.
10. Schmidt, O. Th. Methods Carbohydr. Chem. 1963, 2, 318.
11. Singh, P. P.; Gharia, M. M.; Dasgupta, F.; Srivastava, H. C. Tetrahedron Lett. 1977,
5, 439.
12. Lal, B.; Gidwani, R. M.; Rupp, R. H. Synthesis 1989, 711.
13. Manzo, E.; Barone, G.; Parrilli, M. Synlett 2000, 887.
14. Rauter, A. P.; Ramôa-Ribeiro, F.; Fernandes, A. C.; Figueiredo, J. A. Tetrahedron
1995, 51, 6529.
Nevertheless, for most of the carbohydrate derived isopropylid-
enes, the spiro-fused isopropylidene moiety was very stable to-
ward our reaction conditions than both the internal and terminal
isopropylidenes. It has also been observed that the reaction condi-
tion is very much compatible toward acid labile functionalities,
such as OTHP (entry 3, Table 3), OBn (entry 4, 8, Table 3), OAc (en-
try 9, Table 3) and OBz (entry 10, Table 3). It is interesting to note
that the OTBS group, albeit being more labile than isopropylidenes
under acidic conditions,29 was not hydrolyzed in our reaction con-
ditions and gave considerably good yield of the deisopropylidena-
tion product (entry 6, Table 3).
15. Asakura, J.-I.; Matsubara, Y.; Yoshihara, M. J. Carbohydr. Chem. 1996, 15,
231.
16. Tu, Y.; Wang, Z.-X.; Shi, Y. J. Am. Chem. Soc. 1996, 118, 9806.
In summary, we have developed a simple, efficient, and cata-
lytic method for preparation and removal of O-isopropylidenes
from 1,2-diols using a catalytic amount of phosphotungstic acid
(PTA) as a new catalyst. The same catalyst system was found to
be extremely efficient for chemoselective deacetonation of termi-
nal isopropylidenes in the presence of internal isopropylidenes
upon changing the solvent to acetonitrile-water. Non-toxicity,
availability and low cost of the catalyst; easy handling, purification
and high yields of this protocol are expected to attract attention of
the wider synthetic community.
17. Typical procedure for isopropylidenation of 1, 2-diols:
A suspension of the
substrate (1 mmol) in dry acetone (5 mL)/2,2-dimethoxypropane (2 mmol) in
dry acetone (5 mL) was added 5 mol % of phosphotungstic acid and was stirred
at room temperature under nitrogen atmosphere for the specific time given in
Table 2. After completion of the reaction, the solvent was removed under
reduced pressure. The residue was extracted with dichloromethane
(3 Â 20 mL) and water and the combined organic layer was dried with
Na2SO4 and concentrated in vacuum to give the crude product. The crude
product was purified by column chromatography on Silica gel (60–120 mesh)
with 15–30% ethylacetate in hexane as eluent.
18. Szabo, W. A.; Lee, H. T. Aldrichimica Acta 1980, 13, 13.
19. (a) Barone, G.; Bedini, E.; Iadonisi, A.; Manzo, E.; Parrilli, M. Synlett 2002, 1645;
(b) Chen, M.-Y.; Lu, K. C.; Lee, A. S.-Y.; Lin, C.-C. Tetrahedron Lett. 2002, 43, 2777;
(c) Chen, M.-Y.; Patkar, L. N.; Lu, K. C.; Lee, A. S.-Y.; Lin, C.-C. Tetrahedron 2004,
60, 11465.
Acknowledgments
20. (a) Fleet, G. W. J.; Smith, P. W. Tetrahedron Lett. 1985, 26, 1469; (b) Gerspacher,
M.; Rapoport, H. J. Org. Chem. 1991, 56, 3700; (c) Yadav, J. S.; Chander, M. C.;
Reddy, K. K. Tetrahedron Lett. 1992, 33, 135; (d) Sukumar, M.; Jacques, V.;
Pendri, Y.; Falck, J. R. Tetrahedron Lett. 1986, 27, 2679; (e) Lablance, Y.;
Fitzsimmons, J.; Adams, E. P.; Rokacha, J. J. Org. Chem. 1986, 51, 789; (f) Rawal,
G. K.; Rani, S.; Kumar, A.; Vankar, Y. D. Tetrahedron Lett. 2006, 47, 9117; (g)
Park, K. H.; Yoon, Y. J.; Lee, S. G. Tetrahedron Lett. 1994, 35, 9737; (h) Ichihara,
M. U.; Sakamura, S. Tetrahedron Lett. 1977, 18, 3473.
Thanks are due to UGC, New Delhi [(Grant No. 31-54/2005 (SR)],
CSIR, New Delhi [Grant No. 01(1992)/05/EMR-II] and DST, New
Delhi [Grant No. SR/S1/OC-25/2007] for providing financial support
to carry out this work. SAIF, NEHU is acknowledged for the analyt-
ical data.
21. (a) Iwata, M.; Ohrui, H. Bull. Chem. Soc. Jpn. 1981, 54, 2837; (b) Vijayasaradhi, S.;
Singh, J.; Aidhen, I. S. Synlett 2000, 110; (c) Xiao, X.; Bai, D. Synlett 2001, 535;
(d) Swamy, N. R.; Venkateswarlu, Y. Tetrahedron Lett. 2002, 43, 7549; (e)
Pfrengle, F.; Dekaris, V.; Schefzig, L.; Zimmer, R.; Reissig, H.-U. Synlett 2008, 19,
2965; (f) Procopio, A.; Gaspari, M.; Nardi, M.; Oliverio, M.; Romeo, R.
Tetrahedron Lett. 2008, 49, 1961; (g) Yadav, J. S.; Reddy, B. V. S.; Reddy, S. K.
Chem. Lett. 2001, 430; (h) Reddy, S. M.; Reddy, V.; Venkateswarlu, Y.
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B.; Reddy, N. M.; Yadav, J. S. J. Mol. Catal. 2005, 238, 229; (j) Yadav, J. S.;
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8745.
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Mahender, G.; Ramu, R.; Ramesh, C.; Das, B. Chem. Lett. 2003, 734; (c) Yadav, J.
S.; Raghavendra, S.; Satyanarayana, M.; Balanarsaiah, E. Synlett 2005, 2461; (d)
Chari, M. A.; Syamasundar, K. Synthesis 2005, 708; (e) Agarwal, A.; Vankar, Y. D.
Carbohydr. Res. 2005, 340, 1661.
Supplementary data
Supplementary data associated with this article can be found, in
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