PAPER
O-Isopropylidene Sugar Derivatives
307
Table 1 O-Isopropylidene Derivatives of Miscellaneous Sugarsa (continued)
25
Isopropylidene derivatives Yield(%)
from
Mp (°C)
[a]D
1H NMR (CDCl3)
Elemental Analysis
95
108–109
–18.5 (c = 5.0, H2O)
1.30 (s, 3 H, CH3), 1.35 (s, 3 H, CH3), 1.43 (s, 3 H,
CH3), 1.48 (s, 3 H, CH3), 3.97 (dd, J6a,6b = 8.7 Hz,
O
O
(91)3
(110–111)3 –18.5 (c = 5.0, H2O)3
O
J6a,5 = 5.1 Hz, 1 H, Ha-6), 4.04 (dd, J4,5 = 8.0 Hz, J4,3
2.9 Hz, 1 H, H-4), 4.15 (dd, J6b,6a = 8.7 Hz, J6b,5 = 6.6
Hz, 1 H, Hb-6), 4.25–4.38 (m, 2 H, H-3, H-5), 4.51 (d,
J2,1 = 3.7 Hz, 1 H, H-2), 5.92 (d, J1,2 = 3.7 Hz, 1 H, H-1).
Anal. Calcd for C12H20O6: C, 55.37; H, 7.74. Found:
C, 55.43; H, 7.72.
=
OH
O
O
D-Glucose
95
121–122
+16.6 (c = 2.5, EtOH)
1.32 (s, 3 H, CH3), 1.38 (s, 3 H, CH3), 1.46 (s, 3 H,
CH3), 1.48 (s, 3 H, CH3), 4.03 (dd, J6a,6b = 10.2 Hz,
J6a,5 = 6.1 Hz, 1 H, Ha-6), 4.08 (dd, J6b,6a = 10.2 Hz,
J6b,5 = 6.8 Hz, 1 H, Hb-6), 4.20 (dd, J4,3 = 7.2 Hz,
J4,5 = 3.7 Hz, 1 H, H-4), 4.38–4.44 (m, 1 H, H-5), 4.63
(d, J2,3 = 6.2 Hz, 1 H, H-2), 4.81 (dd, J3,4 = 7.2 Hz,
J3,2 = 6.2 Hz, 1 H, H-3), 5.39 (s, 1 H, H-1).
Anal. Calcd for C12H20O6: C, 55.37; H, 7.74. Found:
C, 55.30; H, 7.73.
O
O
(92)3
(122–123)3 +16.0 (c = 2.6, EtOH)3
O
O
O
OH
D-Mannose
95
Oil
–24.7 (c = 1.1, CHCl3)
1.32 (s, 3 H, CH3), 1.48 (s, 3 H, CH3), 3.55–3.83 (m,
2 H, H-5), 4.40 (br s, 1 H, H-4), 4.57 (d, J2,3 = 6.0 Hz,
1 H, H-2), 4.85 (d, J3,2 = 6.0 Hz, 1 H, H-3), 5.42 (s, 1
H, H-1).
OH
HO
O
(90–93)21a,b (oil)21c
–25.9 (c = 1.1, CHCl3)21c
O
O
Anal. Calcd for C8H14O5: C, 50.52; H, 7.42. Found: C,
50.41; H, 7.39.
D-Ribose
92
70–71
–55.0 (c = 1.1, CHCl3)
–51.0 (c = 0.6, CHCl3)2b
1.33 (s, 3 H, CH3), 1.37 (s, 3 H, CH3), 1.55 (s, 3 H,
CH3), 1.62 (s, 3 H, CH3), 3.83 (dd, J5a,5b = 12.1 Hz,
J5a,4 = 9.7 Hz, 1 H, Ha-5), 4.01 (dd, J5b,5a = 12.1 Hz,
J5b,4 = 7.7 Hz, 1 H, Hb-5), 4.24 (dd, J2,3 = 7.9 Hz,
J2,1 = 5.2 Hz, 1 H, H-2), 4.40–4.53 (m, 2 H, H-3, H-4),
5.43 (d, J1,2 = 5.2 Hz, 1 H, H-1).
O
O
(as by-
(68–69)2b
product) 2b
O
O
O
D-Ribose
Anal. Calcd for C11H18O5: C, 57.38; H, 7.88. Found:
C, 57.50; H, 7.88.
95
80–81
–14.3 (c = 1.5, Me2CO)
–18.1 (c = 1.5, Me2CO)22
1.37 (s, 6 H, CH3), 1.44 (s, 3 H, CH3), 1.51 (s, 3 H,
CH3), 2.31 (t, JOH,1 = 7.5 Hz, 1 H, OH), 3.78 (dd,
J1a,1b = 12.5 Hz, J1a,OH = 7.5 Hz, 1 H, Ha-1), 3.87 (dd,
J1b,1a = 12.5 Hz, J1b,OH = 7.5 Hz, 1 H, Hb-1), 3.92–4.92
(m, 3 H, H-6, H-5),4.32 (d, J4,3 = 1.6 Hz, 1 H, H-4),
4.48 (J4,3 = 1.6 Hz, 1 H, H-3).
O
(96–99)22
(77–78)22
O
O
O
O
OH
L-Sorbose
Anal. Calcd for C12H20O6: C, 55.37; H, 7.74. Found:
C, 55.29; H, 7.76.
97
45–46
+12.7 (c = 1.1; EtOH)
+14.2 (c = unknown;
EtOH)23
1.37 (s, 3 H, CH3), 1.38 (s, 3 H, CH3), 1.42 (s, 12 H,
4 × CH3), 3.69–4.12 (m, 8 H, H-1, H-2, H-3, H-4, H-5,
H-6).
(53)23
(45–46)23
Anal. Calcd for C15H26O6: C, 59.58; H, 8.67. Found:
C, 59.48; H, 8.69.
D-Glucitol
a Literature data within parentheses.
1H NMR spectra were taken on Bruker DRX-400 and Varian Gem-
ini 200 spectrometers. Optical rotations were measured on a Jasco
P-1010 instrument (1.0 dm cell). Combustion analyses were per-
formed on Perkin-Elmer Series II 2400, CHNS analyzer. TLC anal-
yses were carried out on silica gel Merck 60 F254 plates (0.2 mm
layer thickness). Column chromatography was performed on Merck
Kieselgel 60 (70–230 mesh). Anhyd acetone was distilled immedi-
ately before use. Triphenyl phosphine polymer-bound was pur-
chased from Fluka Chemical Co.
Preparation of 1,2:5,6-Di-O-isopropylidene-a-D-glucofuranose;
Typical Procedure
To a magnetically stirred suspension of anhyd polystyryl diphenyl
phosphine (1.12 g, ca. 3.34 phosphine units) in anhyd acetone (10
mL) at r.t., a solution of I2 (0.85 g, 3.34 mmol) in the same solvent
(30 mL) was added dropwise in the dark and under dry N2 atmo-
sphere. After 15 min, solid D-glucopyranose (0.33 g, 1.67 mmol)
was added in one portion to the suspension. TLC monitoring
(CHCl3–MeOH, 9:1) showed that the starting sugar was completely
consumed within 30 min. The reaction mixture was then filtered
Synthesis 2006, No. 2, 305–308 © Thieme Stuttgart · New York