1864
Krüger, Pyplo-Schnieders, Redlich, Winkelmann:
(arom . H), 101.29 (ben zyliden e-C), 84.17 (C-1), 78.11, 73.16, 70.67, 70.13 (C-5, C-4, C-3,
C-2), 68.17 (C-6), 20.79, 20.69 (OCOCH3).
Triph en ylm eth yl 2,3-Di-O-ben zyl-4,6-O-ben zyliden e-1-th io-β-D-glucopyran oside (41)
Com poun d 40 (600 m g, 1.14 m m ol) was ben zylated accordin g to Gen eral procedure 3. Th e
crude product was purified by colum n ch rom atograph y (CH/EA = 15/1). Yield 765 m g
(95%), colorless solid, m .p. 89 °C, [α ]2D0 +34.9 (c 1.0 in CHCl3). For C46H42O5S (706.9) calcu-
lated: 78.16% C, 5.99% H; foun d: 78.29% C, 6.12% H. 1H NMR (300 MHz, CDCl3):
7.14–7.48 m , 30 H (arom . H); 5.42 s, 1 H (ben zyliden e-H); 5.08 d, 1 H, J = 9.8 (Ph CH2);
4.95 d, 1 H, J = 9.8 (Ph CH2); 4.89 d, 1 H, J = 10.2 (Ph CH2); 4.76 d, 1 H, J = 10.2 (Ph CH2);
4.16 d, 1 H, J(1,2) = 9.4 (H-1); 3.75 dd, 1 H, J(5,6′) = 4.8, J(6,6′) = 9.8 (H-6′); 3.66 dd, 1 H,
J(3,4) = 7.6, J(4,5) = 9.0 (H-4); 3.36–3.56 m , 3 H (H-6, H-3, H-2); 2.61 ddd, 1 H, J(4,5) = 9.0,
J(5,6) = 9.0, J(5,6′) = 4.8 (H-5). 13C NMR (75 MHz, CDCl3): 144.54 (CPh 3), 138.36, 138.14,
137.28 (Ci), 129.89–125.86 (arom . H), 100.86 (ben zyliden e-C), 85.73 (C-1), 83.20, 81.32,
81.18 (C-2, C-3, C-4), 76.21, 75.14 (Ph CH2), 69.62 (C-5), 68.34 (C-6).
2-Ch loroeth yl 4,6-O-Isopropyliden e-1-th io-β-D-glucopyran oside (42)
Com poun d 7 (5.07 g, 11.9 m m ol) was deacetylated accordin g to Gen eral procedure 2. Th e
residue was dissolved in an h ydrous aceton e (400 m l), an d 2,2-dim eth oxypropan e (6 m l,
48.8 m m ol) an d catalytic am oun t of 4-toluen esulfon ic acid were added. After stirrin g over-
n igh t, th e reaction m ixture was n eutralized with con cen trated am m on ia an d th e solution
was con cen trated in vacuo. Th e resultin g residue was extracted with h ot dich lorom eth an e.
After reducin g th e solven t, th e crude product was purified by colum n ch rom atograph y
(CH/EA = 1/1). Yield 2.56 g (72%), colorless syrup, [α ]2D0 –42.6 (c 1.0 in MeOH). For
C
16H23ClO7S (394.9) calculated: 48.67% C, 5.87% H; foun d: 48.52% C, 5.90% H.
Diacetate 1H NMR (300 MHz, CDCl3): 5.12 dd, 1 H, J(1,2) = 10.2, J(2,3) = 9.2 (H-2);
4.93 dd, 1 H, J(2,3) = 9.6, J(3,4) = 9.2 (H-3); 4.52 d, 1 H, J(1,2) = 10.2 (H-1); 3.93 dd, J(5,6) =
5.4, J(6,6′) = 10.9 (H-6); 3.77–3.57 m , 4 H (CH2Cl, H-6′, H-4); 3.37 ddd, J(4,5) = 10.0, J(5,6) =
5.4, J(5,6′) = 10.2 (H-5); 2.96 m , 2 H (SCH2); 2.03, 2.01 2 s, 2 × 3 H (2 × OAc); 1.44, 1.35 2 s,
2 × 3 H (2 × isoprop.-CH3).
Vin yl 2,3-Di-O-ben zyl-4,6-O-isopropyliden e-1-th io-β-D-glucopyran oside (43)
Com poun d 42 (2.56 g, 8.57 m m ol) was ben zylated accordin g to Gen eral procedure 3. Th e
crude product was purified by colum n ch rom atograph y (CH/EA = 10/1). Yield 2.11 g (82%),
colorless crystals, m .p. 61 °C, [α ]D20 +3.5 (c 1.0 in MeOH). For C25H30O5S (442.6) calculated:
67.85% C, 6.83% H; foun d: 67.54% C, 7.11% H. 1H NMR (300 MHz, CDCl3): 7.36–7.25 m ,
10 H (arom . H); 6.47 dd, 1 H, J = 10.0 (=CH2); 5.39 d, 1 H, J = 16.9 (=CH2); 5.34 d, 1 H, J =
10.0 (=CH2); 4.87, 4.74 2 d, 2 × 1 H (Ph CH2); 4.78 s, 2 H (Ph CH2); 4.63 d, 1 H, J(1,2) = 9.7
(H-1); 3.94 dd, 1 H, J(5,6) = 5.4, J(6,6′) = 10.9 (H-6); 3.75 dd, 1 H, J(5,6′) = 9.6, J(6,6′) = 10.9
(H-6′); 3.72 dd, 1 H, J(3,4) = 9.1, J(4,5) = 9.5 (H-4); 3.64 dd, 1 H, J(2,3) = 8.2, J(3,4) = 9.1
(H-3); 3.49 dd, 1 H, J(1,2) = 9.7, J(2,3) = 8.2 (H-2); 3.30 ddd, 1 H, J(4,5) = 9.5, J(5,6) = 5.4,
J(5,6′) = 9.6 (H-5); 1.49, 1.41 2 s, 2 × 3 H (2 × isoprop.-CH3).
Collect. Czech. Chem. Commun. (Vol. 69) (2004)