Z. Hricovíniová, M. Hricovíni / Carbohydrate Research 370 (2013) 1–8
7
JCH2a, CH2b = 13.4 Hz, CH2a (NMe)), 4.73 (d, 1H, CH2b (NMe)), 4.59 (d,
3.66 (d, 1H, H-2). 13C NMR (150.84 MHz, D2O): 128.56, 127.67,
125.86, 120.99 (C6H5 (C-3)), 94.37 (C-1), 78.59 (C-3), 75.32 (C-2),
74.85 (C-5), 71.07 (C-4), 61.43 (C-6).
0
1H, H-2), 4.38 (m, 1H, J4,5 = 8.8 Hz, J5,6 = 2.9 Hz, J5,6 = 7.7 Hz H-5),
4.15 (dd, J6,6 = 8.7 Hz, H-6), 3.99 (dd, 1H, H-60), 3.68 (d, 1H, H-4),
0
1.52 (s, 3H, CH3 (Ip)), 1.43 (s, 3H, CH3 (Ip)), 1.35 (s, 3H, CH3 (Ip)),
1.31 (s, 3H, CH3 (Ip)).13C NMR (150.84 MHz, CDCl3): 113.07 (1,2
CMe2), 109.84 (5,6 CMe2), 104.86 (C-1), 85.36 (C-2), 81.33 (C-4),
79.67 (C-3), 71.76 (C-5), 67.31 (C-6), 26.93, 26.83, 26.28, 24.95
(4 ꢀ CH3 Ip).
4.11. 3-C-Nitromethyl-D-glucose (9)
Yield 95%; ½a 2D0
ꢃ
+26.0 (c = 1, H2O) (24 h); mmax (ATR, diamond):
3336 cmꢁ1 (OH); mas 1549 cmꢁ1 (NO2); ms 1379 cmꢁ1 (NO2); MS
(EI, 70 eV); m/z: 241 [M++H], calcd for C7H13O8N 240; 13C NMR
4.6. 3-C-Cyano-1,2: 5,6-Di-O-isopropylidene-
D
-gluco-furanose19
(150.84 MHz, D2O): 102.43 (C-1bf), 96.82 (C-1
91.27 (C-1 p), 81.02 (C-4bf), 81.02 (C-3 f), 80.27 (C-3bf), 79.82
(C-2bf), 78.77 (C-4 f), 76.86 (CH2bf), 76.86 (CH2 f), 76.64 (C-
3bp), 76.18 (C-2bp), 76.02 (CH2 p), 75.80 (C-3 p), 75.64 (CH2bp),
75.47 (C-2 f), 74.27 (C-5bp), 72.74 (C-4 p), 71.86 (C-4bp), 71.43
(C-2 p), 71.04 (C-5 p), 69.46 (C-5bf), 68.70 (C-5 f), 63.56 (C-
6bf), 63.56 (C-6 f), 61.04 (C-6bp), 60.67 (C-6 p).
af), 93.77 (C-1bp),
(5)
a
a
a
a
Yield 421 mg (41%); Rf = 0.79 (solvent D); ½a D20
ꢃ
+42.0 ? +47.0
a
a
(c = 1, acetone);19 Following analytical data are given for the sake
of completeness: mmax (ATR, diamond): 3365 cmꢁ1 (OH),
1375 cmꢁ1 (CN); MS (EI, 70 eV); m/z: 286 [M++H] calcd for
C13H19O6N 285.2931; 1H NMR (599.84 MHz, CDCl3): 5.97 (d, 1H,
J1,2 = 3.6 Hz, H-1), 4.69 (d, 1H, H-2), 4.34 (m, 1H, J4,5 = 7.6 Hz,
a
a
a
a
a
a
a
4.12. 3-C-Cyano-D-gluco-pyranose (10)
0
J5,6 = 4.3 Hz, J5,6 = 6.3 Hz, H-5), 4.15 (d, 1H, H-4), 4.09 (dd,
J6,6 = 8.8 Hz, H-6), 3.95 (dd, 1H, H-60), 1.51 (s, 3H, CH3 (Ip)), 1.41
Yield 93%; ½a 2D0
ꢃ
+20.0 ? +15.0 (c = 1, H2O) (24 h); mmax (ATR, dia-
0
(s, 3H, CH3 (Ip)), 1.33 (s, 3H, CH3 (Ip)), 1.30 (s, 3H, CH3 (Ip)). 13C
NMR (150.84 MHz, CDCl3): 112.92 (1,2 CMe2), 109.32 (5,6 CMe2),
105.11 (C-1), 85.85 (C-2), 82.75 (C-4), 74.22 (C-3), 71.91 (C-5),
66.34 (C-6), 26.29, 26.12, 25.77, 24.62 (4xCH3 Ip).
mond): 3288 cmꢁ1 (OH),1485 (CN); MS (EI, 70 eV); m/z: 206
[M++H], calcd for C7H11O6N 205.1653; 1H NMR (599.84 MHz,
D2O): 5.23 (d, 1H, H-1
3.87 (dd, 1H, H-6b), 3.81 dd, 1H, H-6
(m, 1H, H-60b), 3.77 (m, 1H, H-2
), 3.72 (m, 1H, H-5b), 3.71 (m,
1H, H-4b), 3.71 (m, 1H, H-4
), 3.41 (d, 1H, H-2b). 13C NMR
(150.84 MHz, D2O): 117.24 (s, CN (C-3)), 94.81 (C-1b), 91.41 (C-
), 77.95 (C-3b), 75.32 (C-3 ), 74.94 (C-5b), 74.32 (C-2b), 72.13
(C-2 ), 70.30 (C-4 ), 70.29 (C-4b), 69.76 (C-5 ), 60.34 (C-6b),
60.16 (C-6 ).
a
), 4.79 (d, 1H, H-1b), 3.90 (m, 1H, H-5
a),
a
), 3.79 (dd, 1H, H-60a), 3.72
a
4.7. Typical procedure for acid hydrolysis
a
A mixture of isopropylidene derivative of 3-C-branched chain
aldose in water and Dowex 50 W X4 resin in the H+ form was stir-
red at 75 °C for 7 h. The resin was filtered off, the filtrate was puri-
fied with charcoal, and evaporated to afford syrupy derivative.
1a
a
a
a
a
a
4.13. Typical procedure for Mo(VI) catalyzed isomerization of
the 3-C-branched chain aldoses
4.8. 3-C-Methyl-b-
D
-allo-pyranose (6)
Yield 96%; ½a 2D0
ꢃ
+9.6 ? +11.0 (c = 1, H2O) (24 h);
m
max (ATR, dia-
4.13.1. In microwave field
mond): 3299 cmꢁ1 (OH), ms 2976 (CH3), mas 2887 (CH3), d 1454
(CH3), d 1373 (CH3); MS (EI, 70 eV); m/z: 195 [M++H], calcd for
C7H14O6 194.1825; 1H NMR (599.84 MHz, D2O): 4.79 (d, 1H,
J1,2 = 8.1 Hz, H-1), 3.86 (m, 1H, H-6), 3.70 (m, 1H, H-5), 3.67 (m,
1H, H-60), 3.33 (d, 1H, J4,5 = 9.9 Hz, H-4), 3.13 (d, 1H, H-2), 1.31 (s,
3H, CH3 (C-3)). 13C NMR (150.84 MHz, D2O): 93.98 (C-1), 74.75
(C-2), 74.49 (C-5), 73.83 (C-3), 70.16 (C-4), 61.44 (C-6), 20.99
(CH3 (C-3)).
To the mixture of branched-chain aldose 6–10 dissolved in
water molybdic acid was added (molar ratio 1:10). The reaction
mixture was exposed to microwave irradiation (300 W) for differ-
ent lengths of time. Samples (0.5 mL) were taken at selected inter-
vals (ꢁ1, 2, 3, 4, 5, 10 min), treated with Amberlite IRA-400 in the
HCO3 form (3 mL) to remove the catalyst. The composition of
the reaction mixture was determined by 1H NMR spectroscopy.
The rest of the reaction mixture was also treated batch-wise with
an excess of the ion-exchange resin, filtered off, washed with
water, and combined filtrates were evaporated. Fractionization of
the syrupy residue by column chromatography on Dowex 50 W
X8 in the Ba2+ form, eluted with water at a flow rate 5 mL/h, affor-
ded two isomeric 3-C-branched derivatives that were fully
characterized.
4.9. 3-C-Vinyl-b-
D-allo-pyranose (7)
Yield 93%; ½a 2D0
ꢃ
+4.0 ? +4.5 (c = 1, H2O) (24 h); mmax (ATR, dia-
mond): 3315 cmꢁ1 (OH), 2996 (@CH), 1641 cmꢁ1 (C@C); MS (EI,
70 eV); m/z: 207 [M++H], calcd. for C8H14O6 206.1932; 1H NMR
0
0
0
0
(599.84 MHz, D2O): 5.84 (dd, 1H, J1 ,2 a = 11.0 Hz, J1 ,2 b = 17.4 Hz,
H-10 vinyl), 5.42 (dd, 1H, J2 a,2 b = ꢂ0.4 Hz, H-20a vinyl), 5.39 (dd,
4.13.2. Conventional conditions
0
0
1H, H-20b vinyl), 4.89 (d, 1H, J1,2 = 8.1 Hz, H-1), 3.86 (dd, 1H,
To the aqueous solution of 3-C-branched chain aldose 6–10
molybdic acid was added (molar ratio 1:10). Reaction mixture
was heated in oil-bath at 90 °C for 10–15 h. The composition of
the reaction mixture was examined by 1H NMR spectroscopy until
the equilibrium mixture was reached. The reaction mixture was
stirred with Amberlite IRA-400 in the HCO3ꢁ form (15 mL). The fil-
trates were concentrated to syrup that was fractionated by column
chromatography.
0
J5,6 = 2.0 Hz, J6,6 = 12.1 Hz, H-6), 3.79 (m, 1H, H-5), 3.69 (dd, 1H,
J5,6 = 5.8 Hz, H-60), 3.52 (d, 1H, J4,5 = 8.0 Hz, H-4), 3.30 (d, 1H,
0
H-2). 13C NMR (150.84 MHz, D2O): 138.66 (–CH Vi), 117.39 (–CH2
Vi), 93.92 (C-1), 77.30 (C-3), 74.37 (C-2), 73.28 (C-5), 68.92 (C-4),
61.38 (C-6).
4.10. 3-C-Phenyl-b-
D-allose (8)
Yield 92%; ½a 2D0
ꢃ
+12.0 ? +8.0 (c = 1, H2O) (24 h);
mmax (ATR, dia-
4.14. 3-C-Methyl-b-D-gluco-pyranose (11)
mond): 3293 cmꢁ1 (OH), 3064, 3029, 2935 cmꢁ1 (CH)Ar, 1601,
1547 cmꢁ1 (C–C)Ar; MS (EI, 70 eV); m/z: 257 [M++H], 77 [C6H5+],
calcd for C12H16O6 256.2518; 1H NMR (599.84 MHz, D2O): 7.55–
7.36 (m, 5H, Ph (C-3)), 5.04 (d, 1H, J1,2 = 7.9 Hz, H-1), 3.94 (m, 1H,
H-5), 3.89 (m, 1H, H-6), 3.88 (m, 1H, H-4), 3.73 (m, 1H, H-60),
Yield 19%; ½a 2D0
ꢃ
+8.6 ? +7.1 (c = 1, H2O) (24 h); mmax (ATR, dia-
mond): 3315 cmꢁ1 (OH), ms 2982 (CH3), mas 2866 (CH3), d 1454
(CH3), d 1371 (CH3); MS (EI, 70 eV); m/z: 195 [M++H], calcd for
C7H14O6 194.1825; 1H NMR (599.84 MHz, D2O): 4.66 (d, 1H,