898
P. Gullapalli et al. / Tetrahedron Letters 51 (2010) 895–898
HOH2C
HO
HOH2C
HO
HOH2C
HO
HOH2C
HO
HOH2C
HO
HOH2C
HO
O
O
O
OH
OH
OH
OH
OH
OH
OH
OH
OH
HO
HO
HO
O
O
O
Me
Me
+12.5
Me
+1.6
Me
-1.0
Me
+85.0
Me
-17.1
+14.0
6-Deoxy-
L-psicose 6L
6-Deoxy-
L-fructose 7L
6-Deoxy-
L-tagatose 5L
1-Deoxy-
L-psicose 4L
1-Deoxy-
L-fructose 3L
1-Deoxy-
L-tagatose 8L
HOH2C
O
HO
HOH2C
O
HO
HOH2C
HOH2C
OH
HO
HOH2C
HOH2C
OH
HO
O
OH
OH
HO
HO
HO
O
OH
OH
OH
OH
OH
HO
HO
O
O
Me
Me
Me
Me
Me
Me
+17.0
-13.0
-2.2*
+1.0
-81.4
-14.7*
6-Deoxy-
D-tagatose 5D
6-Deoxy-
D-psicose 6D
6-Deoxy-
D-fructose 7D
1-Deoxy-
D-psicose 4D
1-Deoxy-
D-fructose 3D
1-Deoxy-
D-tagatose 8D
Scheme 8. Specific rotations ½a D20
ꢀ
(c 1.0, H2O), of enantiomeric deoxyketoses. From Ref. 18.
*
9. Izumori, K.; Jenkinson, S. F.; Watkin, D. J.; Fleet, G. W. J. Acta Crystallogr., Sect. E
2007, 63, o1882–o1884.
10. Gullapalli, P.; Shiji, T.; Rao, D.; Yoshihara, A.; Morimoto, K.; Takata, G.; Fleet, G.
W. J.; Izumori, K. Tetrahedron: Asymmetry 2007, 18, 1995–2000.
exquisite stereoselectivity of IK7 to be exploited in the synthesis of
ten hitherto inaccessible deoxyketoses by only three reagents. This
Letter describes the synthesis from rhamnose 1L of the enantio-
mers of 1- and 6-deoxy psicose and fructose [3D, 3L, 4D, 4L, 6D,
11. Whereas
related to
terminal C; this stereochemical motif is referred to in the Letter as t-RR [t for
terminal C]. Alditols similarly related to -threitol are described as t-RS,
whereas -erythritol is t-SS and -threitol is t-SR.
D
-erythrose has R configuration at C3 and S at C2, any higher alditol
-erythritol will have R configuration at both carbons adjacent to the
D
6L, and 7D, 7L] as well as 1-deoxy-
atose 5L—whose enantiomers 8D and 5L may be synthesized from
E. agglomerans 221e oxidation [recognizing t-SR motif] of
1-deoxy- -galactitol 13D and 1-deoxy- -galactitol 13L, respec-
L-tagatose 8L and 6-deoxy-L-tag-
D
L
L
a
12. (a) Deppenmeier, U.; Hoffmeister, M.; Prust, C. Appl. Microbiol. Biotechnol. 2002,
60, 233–242; (b) Kulhanek, M. Adv. Appl. Microbiol. 1989, 34, 141–181; (c) De
Ley, J.; Kersters, K. Bacteriol. Rev. 1964, 28, 164–180.
13. (a) Reichstein, T.; Grüssner, A. Helv. Chim. Acta 1934, 17, 311–328; (b) Hancock,
R. D.; Viola, R. Trends Biotechnol. 2002, 20, 299–305.
D
L
tively. This Letter shows that the concept of Izumoring may be
extended to produce deoxyhexoses.
14. (a) Izumori, K.; Tsuzaki, K. J. Ferment. Technol. 1988, 66, 225–227; (b) Izumori,
K.; Yamakita, M.; Tsumura, T.; Kobayashi, H. J. Ferment. Bioeng. 1990, 70, 26–
29; (c) Rahman, A. K.; Tokunaga, H.; Yoshida, K.; Izumori, K. J. Ferment. Bioeng.
1991, 72, 488–490; (d) Muniruzzaman, S.; Tokunaga, H.; Izumori, K. J. Ferment.
Bioeng. 1995, 9, 323–327; (e) Takeshita, K.; Shimonishi, T.; Izumori, K. J.
Ferment. Bioeng. 1996, 81, 212–215; (f) Sasahara, H.; Mine, M.; Izumori, K. J.
Ferment. Bioeng. 1998, 85, 84–88; (g) Bhuiyan, S. H.; Ahmed, Z.; Utamura, M.;
Izumori, K. J. Ferment. Bioeng. 1998, 86, 513–516; (h) Sasahara, H.; Izumori, K. J.
Biosci. Bioeng. 1999, 87, 548–550; (i) Ahmed, Z.; Shimonishi, T.; Bhuiyan, S. H.;
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Mizanur, R. M.; Takeshita, K.; Moshino, H.; Takata, G.; Izumori, K. J. Biosci.
Bioeng. 2001, 92, 237–241.
Acknowledgment
This work was supported in part by the Program for Promotion
of Basic Research Activities for Innovative Biosciences (PROBRAIN).
Supplementary data
Supplementary data associated with this paper can be found, in
15. Muniruzzaman, S.; Tokunaga, H.; Izumori, K. J. Ferment. Bioeng. 1994, 78, 145–
148.
References and notes
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Jones, N. A.; Jenkinson, S. F.; Wormald, M. R.; Dwek, R. A.; Fleet, G. W. J.;
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K. Enzyme Microb. Technol. 2006, 38, 855–859.
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Fleet, G. W. J.; Izumori, K. J. Biosci. Bioeng. 2008, 106, 473–480.
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Wilson, F. X.; Izumori, K.; Fleet, G. W. J. Tetrahedron Lett. 2009, 50, 3559–3563.
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Hunter, S. J.; Wormald, M. R.; Dwek, R. A.; Izumori, K.; Fleet, G. W. J.
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10
21. For details see Ref. and Supplementary data.
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Acta Crystallogr., Sect. C 2007, 63, o7–o10.
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R. A.; Fleet, G. W. J. Acta Crystallogr., Sect. E 2005, 61, o2949–o2951.
24. Selected data for 6-deoxy-D-psicose 6D: mmax (thin film): 3361 (br s, OH), dH
(D2O, 400 MHz) (A—major anomer): 1.23 (3H, d, MeA, J 6.4), 1.33 (3H, d, MeB, J
6.3), 3.49 (1H, d, H1A, J 12.1), 3.47–3.56 (1H, m, H1B), 3.55 (1H, d, H10A, J 12.1),
3.77–3.82 (2H, m, H10B, HA), 3.98–4.03 (2H, m, 2 ꢂ HB), 4.05–4.14 (3H, m,
2 ꢂ HA, HB); dC (D2O, 100): 18.3 (MeA), 19.9 (MeB), 62.9 (C1B), 64.1 (C1A), 70.9
(CHA), 75.7 (CHB), 75.8 (CHA), 76.7 (CHB), 78.5 (CHA), 79.1 (CHB), 103.6 (C2A),
105.9 (C2B).
25. Jones, N. A.; Jenkinson, S. F.; Soengas, R.; Fanefjord, M.; Wormald, M. R.; Dwek,
R. A.; Kiran, G. P.; Devendar, R.; Takata, G.; Morimoto, K.; Fleet, G. W. J.
Tetrahedron: Asymmetry 2007, 18, 774–786.
26. See Supplementary data for 13C NMR spectra of all the deoxyketoses prepared
in this Letter.