Tandem Epoxidation-Alcoholysis or Epoxidation-Hydrolysis of Glycals
FULL PAPERS
ucts and their stereochemistry were determined by 1H,
13C NMR, COSY, HSQC and DEPT analysis. With complex
Kinfe, D.E De Vos, P. A. Jacobs, B. F. Sels, J. Carbo-
hydr. Chem. 2007, 26, 3, 141.
mixtures, the products were acetylated (Ac2O, pyridine) and
analyzed by NMR.
[3] T. Linker, T. Sommermann, F. Kahlenberg, J. Am.
Chem. Soc. 1997, 119, 9377.
Biphasic reaction using the Venturello compound: To a
solution of 0.01 mmol of Q3PW4O24 in CHCl3 (10 mL) was
added glycal (0.25 mmol), dry NaA (2.5 mg), nucleophile (2
equiv.) and H2O2 (0.375 mmol of 50 wt% solution in H2O;
1.5 equiv. against glycal). The reaction was stirred at 323 K
and monitored by TLC. On completion of the reaction, the
mixture was filtered and the filtrate taken up in CH2Cl2 and
washed 3 times with water. The organic phase was dried
with MgSO4, filtered and concentrated under vacuum, and
then acetylated (Ac2O, pyridine). The identity of products
and the ratio of stereoisomers was determined by analysis of
[4] J.-P. G Seerden, M. M. M. Boeren, H. W. Scheeren, Tet-
rahedron 1997, 53, 34, 1184.
[5] a) R. L. Halcomb, S. J. Danishefsky, J. Am. Chem. Soc.
1989, 111, 6661; b) C. Ernst, M. Piacenza, S. Grimme,
S. Klaffke, Carbohydr. Res. 2003, 338, 231.
[6] a) A. Fꢃrstner, I. Konetzki, J. Org. Chem. 1998, 63,
3072; b) W. J. Sanders, L. L. Kiessling, Tetrahedron
Lett. 1994, 35, 7335; c) L. Shi, Y.-J. Kim, D. Y. Gin, J.
Am. Chem. Soc. 2001, 123, 6939; d) A. B. Charette, J.-F.
Marcoux, B. Cote, Tetrahedron Lett. 1991, 32, 7215;
e) M. Trumtel, P. Tavecchia, A. Veyriꢄres, P. Sinay, Car-
bohydr. Res. 1989, 191, 29; f) T. Vidal, A. Haudrechy,
Y. Langlois, Tetrahedron Lett. 1999, 40, 5677; g) S.-C.
Hung, C.-H. Wong, Angew. Chem. 1996, 108, 2829;
Angew. Chem. Int. Ed. Engl. 1996, 35, 2671; h) M. Car-
pintero, I. Nieto, A. Fernandez-Mayoralas, J. Org.
Chem. 2001, 66, 1768; i) F. Barresi, O. Hindsgual, J.
Am. Chem. Soc. 1991, 113, 9376; j) G. Stork, G. Kim, J.
Am. Chem. Soc. 1992, 114, 1087; k) M. Bols, J. Chem.
Soc. Chem. Commun. 1992, 913.
1
the mixtures by H and 13C NMR, and COSY, HSQC and
DEPT analysis. Where necessary, separation and purification
of products was achieved by chromatography on a column
of silica gel using mixtures of ethyl acetate and hexane as
eluent.
Dihydroxylation using the Venturello compound: To a so-
lution of Q3PW4O24 (0.005 mmol) in 1,4-dioxane (2.5 mL)
(A) or CH3CN (1.5 mL) and EtOAc (1 mL) (B) was added
H2O (0.5 mL), H2O2 (0.190 mmol, 1.5 equiv. against glycal)
and glycal [0.125 mmol dissolved in 0.5 mL 1,4-dioxane (A)
G
[7] G. Bellucci, G. Catelani, C. Chiappe, F. D’Andrea, Tet-
or EtOAc (B)]. The reaction was stirred at 323 K and moni-
tored by TLC. When the reaction was complete, the mixture
was diluted with EtOAc, dried with MgSO4, filtered and
concentrated under reduced pressure. The crude mixture
was acetylated (Ac2O, pyridine) and the mixture of products
analyzed by 1H NMR and 13C NMR spectroscopy, using
COSY, HSQC and DEPT analysis.
rahedron Lett. 1994, 35, 45, 8433.
[8] E. Honda, D. Y. Gin, J. Am. Chem. Soc. 2002, 124,
7343.
[9] a) C.-J. Liu, W.-Y. Yu, S.-G. Li, C.-M. Che, J. Org.
Chem. 1998, 63, 7364; b) X.-Q. Yu, J.-S. Huang, W.-Y.
Yu, C.-M. Che, J. Am. Chem. Soc. 2000, 122, 5337.
[10] a) G. Soldaini, F. Cardona, A. Goti, Tetrahedron Lett.
2003, 44, 5589; b) G. Soldaini, F. Cardona, A. Goti,
Org. Lett. 2005, 7, 725; c) A. Goti, F. Cardona, G. Sol-
daini, C. Crestini, C. Fiani, R. Saladino, Adv. Synth.
Catal. 2006, 348, 476.
Acknowledgements
[11] E. C. Boyd, R. V. H. Jones, P. Quayle, A. J. Waring,
This research is supported by the National Research Founda-
tion (South Africa) and the Flemish Government (Bilateral
Scientific Cooperation). The authors wish to further thank
CECATand the GOA program (KU Leuven) and IAP (Bel-
gian Federal Government) for funding.
Green Chem. 2003, 5, 679.
[12] V. Bilik, S. Kucar, Carbohydr. Res. 1970, 13, 311.
[13] S. Rani, Y. D. Vankar, Tetrahedron Lett. 2003, 44, 907.
[14] P. Tiwari, A. K. Misra, J. Org. Chem. 2006, 71, 2911.
[15] P. Levecque, D. Gammon, H. H Kinfe, P. Jacobs, D.
De Vos, B. Sels, Org. Biomol. Chem. 2007, 5, 1800.
[16] R. W. Friesen, S. J. Danishefsky, J. Am. Chem. Soc.
1989, 111, 6656–6660.
References
[17] R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations
of Organic Compounds, Academic Press, New York,
1981.
[1] a) Special Issue on Carbohydrates and Glycobiology,
Science 2001, 291, 2263; b) A. Varki, Glycobiology
1993, 3, 97; c) R. A. Dwek, Chem. Rev. 1996, 96, 683;
d) Y. C. Lee, R. T. Lee, Acc. Chem. Res. 1995, 28, 8,
321; e) S. J. Danishefsky, M. T. Bilodeau, Angew. Chem.
Int. Ed. Engl. 1996, 35, 1380; f) D. W. Gammon, B. F.
Sels, in: Handbook of Chemical Glycosylation, (Ed.:
A. V. Demchenko), Wiley-VCH, Weinheim, 2008.
[2] a) R. U. Lemieux, S. Levine, Can. J. Chem. 1964, 42,
1473; b) J. Thiem, H. Karl, J. Schwetner, Synthesis
1978, 696; c) C. H. Marzabadi, C. D. Spilling, J. Org.
Chem. 1993, 58, 3761; d) B. Sels, P. Levecque, R. Bro-
sius, H. Kinfe, D. De Vos, D. Gammon, P. Jacobs, Adv.
Synth. Catal. 2005, 347, 93; e) D. W. Gammon, H. H.
Kinfe, D. E. De Vos, P. A. Jacobs, B. F. Sels, Tetrahe-
dron Lett. 2004, 45, 9533; f) D. W. Gammon, H. H.
[18] M. Chmielewski, I. Fokt, J. Grodner, G. Grynkiewicz,
W. Szeja, J. Carbohydr. Chem. 1989, 8, 735.
[19] J. P. Lellouche, S. Koeller, J. Org. Chem. 2001, 66, 693.
[20] a) I. D. Blackburne, P. M. Fredericks, R. D. Guthrie,
Aust. J. Chem. 1976, 29, 381; b) desilylation with 1.5
equiv. TBAF in THF (10 mLmmolꢀ1).
[21] S. K. Madhusudan, G. Agnihotri, D. S. Negi, A. K.
Misra, Carbohydr. Res. 2005, 340, 1373.
[22] a) M. L. Wolfrom, A. Thompson, Methods in Carbohy-
drate Chemistry II: Reactions with Carbohydrates, Aca-
demic Press, New York, 1962, p 211; b) H. W. Fletcher,
Methods in Carbohydrate Chemistry II: Reactions with
Carbohydrates, Academic Press, New York, 1962,
Adv. Synth. Catal. 2008, 350, 1557 – 1568
ꢂ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1567