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Table 1 Consecutive protection/glycosylation reactions. It is noted that protec-
tion products 6, 7 and 11 can function as glycosyl donors or as acceptors after
specific deprotection (e.g. conversion of 6 to 16/17). Different colours are used to
designate individual reactions
Isolated
yield
Entry
1
Product
Bz2O,
Et3N
—
—
—
73%
2
3
4
BnBr,
NaH
67%
64%
50%
Ac2O,
Et3N
Ac2O,
Et3N
5
6
Bz2O,
Et3N
52%
50%
Scheme 2 Synthetic procedures to prepare oligomannosides 1, 3, 4 and 5.
5 (a) L. Kremer, V. Briken, S. A. Porcelli and G. S. Besra, Mol.
Microbiol., 2004, 53, 391; (b) E. H. Song, A. O. Osanya,
C. A. Petersen and N. L. Pohl, J. Am. Chem. Soc., 2010, 132, 11428.
6 (a) A. V. Demchenko, General Aspects of the Glycosidic Bond Formation
in Handbook of Chemical Glycosylation, ed. A. V. Demchenko, Wiley-
VCH, Weinheim, 2008, p. 1; (b) S.-G. Lee, J. M. Brown, C. J. Rogers,
J. B. Matson, C. Krishnamurthy, M. Rawat and L. C. Hsieh-Wilson,
BnBr,
NaH
7
BnBr,
NaH
52%
¨
Chem. Sci., 2010, 1, 322; (c) A. Adibekian, P. Bindschadler, M. S. M.
Timmer, C. Noti, N. Schu¨tzenmeister and P. H. Seeberger, Chem.–
Eur. J., 2007, 13, 4510; (d) S. Arungundram, K. Al-Mafraji, J. Asong,
F. E. Leach III, M. Amster, A. Venot, J. E. Turnbull and G.-J. Boons,
J. Am. Chem. Soc., 2009, 131, 17394; (e) M. R. Pratt and C. R. Bertozzi,
Org. Lett., 2004, 6, 2345; ( f ) J. Dinkelaar, H. Gold, H. S. Overkleeft,
´
J. D. C. Codee and G. A. van der Marel, J. Org. Chem., 2009, 74, 4208;
a
Thiomannoside 10 (1.0 eq.) in CH2CI2 was treated with PhC(OMe)3
(g) Y.-P. Hu, S.-Y. Lin, C.-Y. Huang, M. M. L. Zulueta1, J.-Y. Liu,
W. Chang and S.-C. Hung, Nat. Chem., 2011, 3, 557; (h) C.-C. Wang,
M. M. L. Zulueta1 and S.-C. Hung, Chimia, 2011, 65, 54.
b
(3.0 eq.), CSA. Two methods were applied to protect the C4-hydroxyl
group. To form an ester, Ac2O (or Bz2O, 2.0 eq.) and Et3N (3.0 eq.) in
CH2CI2 were used. To form an ether, BnBr (2.0 eq.) and NaH (4.0 eq.) in
THF were utilized. The reaction mixture was treated with LevOH
(1.5 eq.) and EDC (1.5 eq.) in CH2CI2. For entries 4–7, 1.0 eq. of glycosyl
donor (11, 6, 7 or 7) reacted with an acceptor [15 (1.5 eq.), (15 (1.5 eq.), 16
(0.5 eq.) or 17 (0.25 eq.), respectively] in CH2CI2 at ꢀ40 1C in the presence
of NIS (2.0 eq.), TfOH (0.2 eq.) and 3 Å molecular sevies.
7 (a) O. Kanie, Y. Ito and T. Ogawa, J. Am. Chem. Soc., 1994, 116, 12073;
(b) T. Takahashi, H. Yamada and T. Kato, Tetrahedron Lett., 1999,
40, 4581; (c) J. A. Watt and S. J. Williams, Org. Biomol. Chem., 2005,
3, 1982; (d) P. H. Seeberger, D. M. Ratner and O. J. Plante, Eur. J. Org.
Chem., 2002, 826; (e) F. A. Jaipuri and N. L. Pohl, Org. Biomol. Chem.,
2008, 6, 2686; ( f ) H. K. Lee, C. N. Scanlan, C. Y. Huang, A. Y. Chang,
D. A. Calarese, R. A. Dwek, P. M. Rudd, D. R. Burton, I. A. Wilson and
C. H. Wong, Angew. Chem., Int. Ed., 2004, 43, 1000; (g) A. A. Abdo and
M. Ziegler, et al., Science, 2011, 331, 739; (h) M. Hagiwara, M. Dohi,
Y. Nakahara, K. Komatsu, Y. Asahina, A. Ueki, H. Hojo, Y. Nakahara
and Y. Ito, J. Org. Chem., 2011, 76, 5229.
8 (a) I. Marın, J. Castilla, M. Isabel Matheu, Y. Dıaz and S. Castillon,
J. Org. Chem., 2011, 76, 9622; (b) M. Emmadi and S. S. Kulkarni,
J. Org. Chem., 2011, 76, 4703; (c) D. Crich, L. Li and M. Shirai, J. Org.
Chem., 2009, 74, 2486; (d) J. J. Reina and J. Rojo, Tetrahedron Lett.,
2006, 47, 2475.
c
d
On the basis of this development, we have been preparing various
fully deprotected oligomannosides (e.g. 5) for examining their
biological activities. The result will be reported in due course.
´
´
Notes and references
1 K. Pekari, D. Tailler, R. Weingart and R. R. Schmidt, J. Org. Chem.,
2001, 66, 7432.
9 V. Pozsgay, J. Org. Chem., 1999, 64, 7277.
2 B. Cao, J. M. White and S. J. Williams, Beilstein J. Org. Chem., 2011, 7, 369. 10 Z. Tu, H.-W. Hsieh, C.-M. Tsai, S.-G. Wang, C.-W. Hsu, K.-J. Wu,
3 J. Lehmann and U. P. Weitzel, Carbohydr. Res., 1996, 294, 65. K.-I. Lin and C.-H. Lin, submitted.
4 I. Botos, B. R. O’Keefe, S. R. Shenoy, L. K. Cartner, D. M. Ratner, 11 Formation of allyl ether led to a lower yield due to a small extent
P. H. Seeberger, M. R. Boyd and A. Wlodawer, J. Biol. Chem., 2002,
277, 34336.
of decomposition if acetate or benzoate existed in the same
molecule.
c
This journal is The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 4265--4267 4267