3
yields to produce 1-deoxy disaccharides. Herein, aqueous ethanol
was employed to dissolve the disaccharide-based DTCs. As
expected, longer reaction times were required for relatively high
conversions of disaccharide-based DTCs (entries 4-6).
4.
Savel’ev, A. N.; Ibatyllin, F. M.; Eneyskaya, E. V.; Kachurin, A.
M.; Neustroev, K. N. Carbohydr. Res. 1996, 296, 261.
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5
6
.
.
7
8
.
(a) Xie, X.; Wang, G. J. Org. Chem.2005, 70, 8687; (b) Ella-
Menye, J.; Xie X.; Wang, G. Carbohydr. Res.2008, 343, 1743; (c)
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Guiry, K. P.; Coles, S. J.; Moynihan, H. A.; Lawrence, S. E. Cryst.
Growth Des. 2008, 8, 3927.
Table 2
.
.
Synthesis of 1-deoxy monosacchrides and 1-deoxy disaccharides.a
9
1
Murali, R.; Nagarajan, M. Carbohydr. Res. 1996, 280, 351.
AIBN (1.0 equiv)
H PO (5 equiv)
NaHCO3 (6 equiv)
0. Readman, S. K.; Marsden, S. P.; Hodgson, A. Synlett 2000, 11,
1628.
1. Ness, R. K.; Fletcher, Jr., H. G.; Hudson, C. S. J. Am. Chem. Soc.
3
2
(
OH)n
(OH)n
O
O
1
S
NMe2
H
1
950, 72, 4547.
o
Solvent, 75 C
H
S
1
1
2. Kocienski, P.; Pant, C. Carbohydr. Res. 1982, 110, 330.
3. Ruttens, B.; Blom, P.; Hoof, S. V.; Hubrecht, I.; Eycken, J. V. J.
Org. Chem. 2007, 72, 5514.
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Yuan, C.; Hollingsworth, R. I. Tetrahedron Lett. 2011, 52, 5421.
Entry
1
Product
Solvent
EtOH
Time/h
1
Yield/%b
90
1
OH
OH
O
HO
HO
15. Uchiyama, T.; Shishikura, K.; Ogawa, K.; Ohshima, Y.; Miyairi,
S. Tetrahedron Lett. 2016, 57, 5294.
6. Giese, B. Pure Appl. Chem. 1988, 60, 1655.
17. McMaster, C.; Bream , R. N.; Grainger, R. S. Org. Biomol. Chem.
2012, 10, 4752.
8. (a) Surzur, J. M.; Teissier, P. C. R. Acad. Sci. Fr. Ser. C 1967,
264, 1981; (b) Tanner, D. D.; Law, F. C. P. J. Am. Chem. Soc.
1
-deoxy mannose
1
O
HO
HO
2
OH
EtOH
EtOH
1
1
4
90
90
95
1-deoxy xylose
1
HO OH
O
1
969, 91, 7535.
3c
4
HO
OH
19. (a) Noguchi, M.; Tanaka, T.; Gyakushi, H.; Kobayashi, A.; Shoda,
S. J. Org. Chem. 2009, 74, 2210; (b) Tanaka, T.; Matsumoto, T.;
Noguchi, M.; Kobayashi, A.; Shoda, S. Chem. Lett. 2009, 38, 458;
(c) Tanaka, T.; Nagai, H.; Noguchi, M.; Kobayashi, A.; Shoda, S.
Chem. Commun. 2009, 3378; (d) Tanaka, T.; Huang, W. C.;
Noguchi, M.; Kobayashi, A. Shoda, S. Tetrahedron Lett. 2009, 50,
2154; (e) Yoshida, N.; Noguchi, M.; Tanaka, T.; Matsumoto, T.;
Aida, N.; Ishihara, M.; Kobayashi, A.; Shoda, S. Chem. Asian J.
2011, 6, 1876; (f) Noguchi, M.; Fujieda, T.; Huang, W. C.;
Ishihara, M.; Kobayashi, A.; Shoda, S. Helv. Chim. Acta 2012, 95,
1928; (g) Li, G.; Noguchi, M.; Kashiwagura, H.; Tanaka, Y.;
Serizawa, K.; Shoda, S. Tetrahedron Lett. 2016, 57, 3529; (h)
Alexander, S. R.; Fairbanks, A. J. Org. Biomol. Chem. 2016, 13,
6679; (i) Alexander, S. R.; Lim, D.; Amso, A.; Brimble, M. A.;
Fairbanks, A. J. Org. Biomol. Chem. 2017, 15, 2152; (j) Lim, D.;
Fairbanks, A. J. Chem. Sci. 2017, 8, 1896; (k) Novoa, A.;
1-deoxy galactose
HO OH
OH
O
O
EtOH/H O
O
2
HO
HO
OH
(5/1)
OH
1-deoxy lactose
HO OH
O
HO
OH
O
EtOH/H O
2
5
6
8
4
85
90
O
HO
HO
(4/1)
OH
1
-deoxy melibiose
OH
OH
O
HO
O
O
HO
EtOH/H O
HO
2
NHAc
NHAc
(
4/1)
1
-deoxy chitobiose
Barluenga, S.; Serba , C.; Winssinger, N. Chem. Commun. 2013,
4
9, 7608; (l) Tanaka, H.; Yoshimura, Y.; Jørgensen, M. R.;
Cuesta-Seijo, J. A.; Hindsgaul, O. Angew. Chem. Int. Ed. 2012,
1, 11531; (m) Köhling, S.; Exner, M. P.; Nojoumi, S.; Schiller,
J.; Budisa, N.; Rademann, J. Angew. Chem. Int. Ed. 2016, 55,
5510; (n) Köhling, S.; Künze, G.; Lemmnitzer, K.; Bermudez,
a
Reaction donditions: see the Supporting Information; Monosaccharides,
c
0
.1M; Disaccharides 0.05M; bIsolated yield; N,N-diethyl galatopyranosyl
dithiocarbamate was used as a starting material.
5
1
In summary, we have found an extremely facile synthetic
protocol for 1-deoxy sugars where one-step preparable
unprotected glycosyl dithiocarbamates (Gly-DTCs) are
desulfurized in high yields through glycosyl radicals. The AIBN-
M.; Wolber, G.; Schiller, J.; Huster, D.; Rademann, J. Chem. Eur.
J. 2016, 22, 5563.
20. (a) Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin
Trans. 1 1975, 16, 1574. (b) Barton, D. H. R.; Dorchak, J.;
Jaszberenyi, J. C. Tetrahedron 1992, 48, 7435.
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Lett. 1992, 33, 5709; (b) Boivin, J.; Jrad, R.; Juge, S.; Nguyen, V.
T. Org. Lett., 2003, 5, 1645; (c) Perchyonok, V. T.; Tuck, K. L.;
Langford, S. J.; Hearn, M. W. Tetrahedron Lett. 2008, 49, 4777.
3 2 3
H PO -NaHCO conditions provide a green approach. The
2
synthesis can be achieved under mild reaction conditions without
protecting groups and in the absence of strong acids or bases.
This is the first protection-free process for preparation of 1-deoxy
sugars. The present method can be applied to 1-deoxy
oligosaccharides or polysaccharides that will help to elucidate the
role of carbohydrates in metabolic cycles.
22. (a) Yorimitsu, H.; Shinokubo,; Oshima, K. Chem. Lett. 2000, 104.
b) Yorimitsu, H.; Shinokubo, H.; Oshima, K. Bull. Chem. Soc.
(
Jpn. 2001, 74, 225.
2
3. (a) Bowman, W. R.; Krintel, S. L.; Schilling, M. B. Org. Biomol.
Chem. 2004, 2, 585; (b) Barks, J. M.; Gilbert, B. C.; Parsons, A.
F.; Upeandran, B. Tetrahedron Lett. 2001, 42, 3137; (c) A. Studer
Acknowledgments
,
S. Amrein, Angew. Chem. Int. Ed. 2000, 39, 3080.
4. Thavasi, V.; Bettens, R. P. A.; Leong, L. P.J. Phys. Chem. A 2009,
13, 3068.
2
This work was supported by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports,
Science and Technology, Japan. We thank Mr. Keisuke Hokotate
for experimental support.
1
Supplementary Material
Supplementary material is available: Additional experimental
and characterization details, NMR spectra and ESI-MS data of
products.
References and notes
1
2
3
.
.
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Dills, W.L.; Meyer, W. L. Biochemistry 1976, 15, 4506.
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Pitkänen, E.; Pitkänen, O. M. Pflug. Arch. Eur. J. Physiol. 1992,
Highlights:
4
20, 367.