R. Luboradzki et al. / Tetrahedron 61 (2005) 10122–10128
10127
0
J6,5Z6.1 Hz, J6,6 Z8.2 Hz, H-6), 4.11 (dd, 1H, J4,3
Z
(d, 1H, H-2), 4.27 (d, 1H, J3,4Z2.9 Hz, H-3), 4.08 (dd, 1H,
J4,5Z7.6 Hz, H-4), 3.88 (m, H-5), 3.74 (dd, 1H, J6,5Z3.4 Hz,
0
2.8 Hz, J4,5Z7.7 Hz, H-4), 3.94 (dd, 1H, J6 ,5Z5.6 Hz,
H-60), 2.55 (d, 1H, JZ3.7 Hz, OH), 1.62 (m, 8H, 4!CH2),
1.34 (m, 16H, 8!CH2), 0.93 (m, 12H, 4!CH3). 13C NMR
(CDCl3) d: 115.98 (O–C–O), 113.60 (O–C–O), 105.86
(C-1), 86.01, 82.36, 76.01, 74.00, 68.76 (C-6), 38.01 (CH2),
37.82 (CH2), 37.63 (CH2), 36.98 (CH2), 26.71 (CH2), 26.52
(CH2), 26.40 (CH2), 26.31 (CH2), 23.49 (CH2), 23.44
(CH2), 23.38 (2!CH2), 14.54 (2!CH3), 14.50 (CH3),
14.38 (CH3). HR-MS (ESI) calcd for C24H44NaO6 [MC
Na]C: 451.3030. Found: 451.3054.
J6,6 Z11.7 Hz, H-6), 3.61 (dd, 1H, J6 ,5Z6.2 Hz, H-60),
1.20 (s, 3H, CH3), 0.95 (s, 9H, tert-Bu). 13C NMR (CDCl3C
CD3OD) d: 119.35, 104.78 (C-1), 85.31, 80.66, 74.92,
69.92, 64.36 (C-6), 37.95, 25.18, 22.23. Minor diastereoi-
somer had 1H NMR (CDCl3CCD3OD) d: 5.90 (d, 1H,
0
0
J1,2Z3.7 Hz, H-1), 4.42 (d, 1H, H-2), 4.24 (d, 1H, J3,4
Z
2.7 Hz, H-3), 4.03 (dd, 1H, J4,5Z7.7 Hz, H-4), 3.88 (m,
0
H-5), 3.76 (dd, 1H, J6,5Z3.4 Hz, J6,6 Z11.5 Hz, H-6), 3.57
(dd, 1H, J6 ,5Z6.3 Hz, H-60), 1.37 (s, 3H, CH3), 0.87 (s, 9H,
0
tert-Bu). 13C NMR (CDCl3CCD3OD) d: 116.54, 106.50
(C-1), 88.06, 81.05, 75.13, 69.96, 64.27 (C-6), 40.62, 25.22,
19.05. HR-MS (ESI) calcd for C12H22NaO6 [MCNa]C:
285.1309. Found: 285.1324.
4.3.4. 1,2-O-(1-Propylpentylidene)-a-D-glucofuranose
(6). Slower moving fractions comprised the title compound
(8%, amorphous glass). [a]2D5C0.4 (c 0.7, chloroform/
methanol 9:1). 1H NMR (CDCl3CCD3OD) d: 5.88 (d, 1H,
J1,2Z3.7 Hz, H-1), 4.46 (d, H, H-2), 4.26 (d, 1H, J3,4
Z
4.4. Gelation test procedure
2.4 Hz, H-3), 4.00 (dd, 1H, J4,5Z7.3 Hz, H-4), 3.93 (m, 1H,
0
H-5), 3.78 (dd, 1H, J6,5Z3.2 Hz, J6,6 Z11.7 Hz, H-6), 3.63
The gelation test was carried out as follows: the gelator was
mixed in the closed-capped tube with the appropriate amount
of solvent to result in a concentration of 3% [g mLK1] (about
15 mg of gelator and 0.5 mL of solvent were used). The
mixture was heated until the solid was dissolved and then
about one further minute. By this procedure usually the
solvent bp was reached. The test tube was cooled in air to
20 8C, left for 24 h at this temperature and then turned
upside down. When the gel was formed the whole procedure
was repeated with the concentration below 1%. Once we
found by chance the gel formation in 5/ethyl acetate system
in concentration over 3% (while at 3% it was marked as ‘S’)
all the ‘S’ marked systems in Table 1 (solution in 3%) were
checked in higher concentration until we get either G (S/
G) or P (S/P). In some cases, however, the solubility was
so high and the amount of the gelator limited that a final
answer cannot be given. In the case of ‘I’ at starting 3%
concentration the lower concentrations were used in order to
fully dissolve the saccharide, as the presence of the crystals
can influence gelation (to get finally either I/G or I/P).
All gels were also, in addition to usual ‘invert vial test’,
examined using an optical microscope to exclude self-
supporting precipitation.
(dd, 1H, J6 ,5Z5.9 Hz, H-60), 1.62 (m, 2H), 1.47 (m, 2H),
0
1.26 (m, 8H), 0.86 (m, 6H). 13C NMR (CDCl3CCD3OD) d:
115.91 (O–C–O), 105.32 (C-1), 85.95, 80.67, 75.41, 70.24,
64.43 (C-6), 37.63 (CH2), 37.54 (CH2), 26.65 (CH2), 26.27
(CH2), 23.27 (2!CH2), 14.38 (CH3), 14.32 (CH3). HR-MS
(ESI) calcd for C15H28NaO6 [MCNa]C: 327.1778. Found:
327.1787.
From cycloheptanone (hexane/ethyl acetate 3:2, then ethyl
acetate, then ethyl acetate/methanol 3:1 as eluents) two
products were obtained.
4.3.5. 1,2:5,6-Di-O-cycloheptylidene-a-D-glucofuranose.
Faster moving fractions contained crude title compound
(7%). Mp: 112–114 8C. [a]2D5C13.1 (c 1.7, chloroform). 1H
NMR (CD3OD) d: 5.81 (d, 1H, J1,2Z3.6 Hz, H-1), 4.39 (dd,
1H, J2,3Z0.4 Hz, H-2), 4.25 (m, 1H), 4.10 (m, 1H), 4.03
(dd, 1H, JZ2.8, 11.5 Hz), 4.01 (dd, 1H, J6,5Z6.2 Hz, J6,
6 Z8.6 Hz, H-6), 3.88 (dd, 1H, J6 ,5Z5.8 Hz, H-60),
1.45–1.95 (other protons). 13C NMR (CD3OD) d: 117.4
(C), 114.6 (C), 106.2 (C-1), 86.3, 82.7, 75.3, 73.7, 67.5
(C-6), 41.3 (CH2), 40.9 (CH2), 39.4 (CH2), 38.8 (CH2), 30.4
(CH2), 30.3 (CH2), 30.1 (CH2), 29.9 (CH2), 23.6 (CH2), 23.4
(CH2), 23.3 (CH2), 23.0 (CH2). HR-MS (ESI) calcd for
C20H32NaO6 [MCNa]C: 391.2091. Found: 391.2085.
0
0
4.5. X-ray crystallography
4.3.6. 1,2-O-Cycloheptylidene-a-D-glucofuranose (8).
Slower moving fractions comprised the title compound
(8%). Mp: 149–150 8C (lit. mp: 151.5–152.5 8C)18. 1H
NMR (CD3OD) d: 5.83 (d, 1H, J1,2Z3.7 Hz, H-1), 4.41 (d,
1H, H-2), 4.20 (d, 1H, J3,4Z2.7 Hz, H-3), 3.98 (dd, 1H,
Diffraction data for 7 and 10 were collected at 100 K by
using Kappa CCD diffractometer with graphite monochro-
mated Mo Ka radiation. Lorentz and polarization correc-
tions but not absorption corrections were applied. Structures
were solved by direct methods (SHELXS-97) and refined on
F2 by full-matrix least-squares method (SHELXL-97)19. All
atoms except hydrogens were refined as anisotropic. 7:
triclinic, space group P1, aZ5.5010(3), bZ6.1960(4), cZ
J4,5Z8.6 Hz, H-4), 3.87 (m, 1H, H-5), 3.74 (dd, 1H, J6,5
Z
0
0
3.2 Hz, J6,6 Z11.6 Hz, H-6), 3.58 (dd, 1H, J6 ,5Z6.0 Hz,
H-60), 1.5–1.98 (m, other protons). 13C NMR (CD3OD) d:
117.2 (C), 106.1 (C-1), 86.0, 81.3, 75.5, 70.4, 65.2 (C-6),
41.1 (CH2), 39.4 (CH2), 30.1 (CH2), 29.9 (CH2), 23.4 (CH2),
23.0 (CH2).
˚
10.4990(7) A, aZ79.285(3), bZ85.502(4), gZ65.609(4)8,
3
˚
VZ320.23(3) A , R1Z0.042 [IO2s(I)], wR2Z0.094 (all
data), 10: monoclinic, space group C2, aZ10.0600(8), bZ
˚
5.6470(3), cZ20.5190(16) A, bZ100.637(3)8, VZ
3
˚
4.3.7. 1,2-O-(1,2,2-Trimethylpropylidene)-a-D-glucofur-
anose (14) (as a mixture of diastereoisomers). The title
compound was obtained from 3,3-dimethyl-2-butanone
(pinacolone). Hexane/ethyl acetate 7:3, then ethyl acetate
1145.63(14) A , R1Z0.042 [IO2s(I)], wR2Z0.097 (all
data). Crystallographic data for compounds 7 and 10 have
been deposited with the Cambridge Crystallographic Data
Centre as supplementary publications no. CCDC268574 and
CCDC268575, respectively. Copies of the data can be
obtained free of charge, on application to CCDC, 12 Union
1
as eluents, yield 8%. Major diastereoisomer had H NMR
(CDCl3CCD3OD) d: 5.87 (d, 1H, J1,2Z3.8 Hz, H-1), 4.48