Inhibitors of Galactosyltransferases
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trated. Th e residue was ch rom atograph ed on a colum n of silica gel in th e system petroleum
eth er–AcOEt (1:4). Ph osph on ates 12 an d 13 (0.74 g, 37%) were obtain ed as an in separable
m ixture followed by dieth yl [(1E,3E,5R,6R)-3,5,7-tris(ben zyloxy)-6-h ydroxyh epta-1,3-dien -
1-yl]ph osph on ate (14) (0.20 g, 0.4 m m ol, 14%). 1H NMR (500 MHz, CDCl3): 7.30–7.25 m ,
6 H (H-arom ); 6.95 dd, 1 H, J(6,7) = 17.1, J(6,P) = 21.8 (H-6); 6.02 dd, 1 H, J(7,6) = 17.4,
J(7,P) = 18.5 (H-7); 5.45 d, 1 H, J(4,3) = 9.6 (H-4); 4.70 s, 2 H (CH2Ph ); 4.52–4.46 m , 3 H
(CH2Ph ); 4.42 dd, 1 H, J(3,4) = 9.6, J(3,2) = 5.4 (H-3); 4.24 d, 1 H J(gem ) = 11.7 (CH2Ph );
4.14–4.05 m , 4 H (OCH2); 3.70 dd, 1 H, J(2,3) = 10.4, J(2,1) = 5.2 (H-2); 3.47 d, 2 H, J(1,2) =
5.2 (H-1, H-1′); 1.35 t, 6 H, J(CH3CH2) = 7.0 (CH3). 13C NMR: 154.86 d, J(5,P) = 23.9 (C-5);
143.43 d, J(6,P) = 6.9 (C-6); 137.94 (2 × quatern ary C-arom ); 136.47 (quatern ary C-arom );
128.56–127.57 (CH-arom ); 122.78 (C-4); 116.21 d, J(7,P) = 190.7 (C-7); 74.35, 73.50
(CH2Ph ); 73.29 (C-3); 72.97 (C-2); 70.70 (CH2Ph , C-1); 62.00 d, J(H,P) = 5.4 (OCH2); 16.37 d,
J(H,P) = 5.6 (CH3). 31P NMR: 18.87. For C32H39O7P (566.6) calculated: 67.83% C, 6.94% H;
foun d: 68.00% C, 7.02% H.
3,4,5,7-Tetra-O-ben zyl-1,2-dideoxy-D-galacto-h ept-1-en itol (15)
Method A. To a suspen sion of MePh 3PBr (2.34 g, 6.5 m m ol) in THF (15 m l), un der argon ,
butyllith ium (1.6 M in h exan e, 4.9 m l, 7.8 m m ol) was added dropwise. After 30 m in of vig-
orous stirrin g, a solution of 2,3,4,6-tetra-O-ben zyl-D-galactopyran ose (1.23 g, 2.3 m m ol) in
THF (12 m l) was added; th e m ixture was h eated at 60 °C an d stirred for 3 h . Th e organ ic
layer was th en wash ed several tim es with saturated aqueous Na2CO3 an d th e com bin ed
aqueous layers were extracted with dieth yl eth er. Th e com bin ed organ ic layers were dried
over an h ydrous Na2SO4 an d con cen trated. Th e resultin g syrup was subjected to silica gel
ch rom atograph y in system petroleum eth er–AcOEt (4:1) to afford th e m ain product 15
(0.32 g, 0.6 m m ol, 26%), [α]D –6.8 (c 1.1, CHCl3). 1H NMR (500 MHz, CDCl3): 7.34–7.17 m ,
20 H (H-arom ); 5.87 ddd, 1 H, J(2,3) = 7.9 (H-2); 5.87 d, 1 H, J(1′,2) = 17.4 (H-1′); 5.29 d,
1 H, J(1,2) = 10.4 (H-1); 4.75 s, 2 H (CH2Ph ); 4.64 d, 1 H, J(gem ) = 11.8 (CH2Ph ); 4.47 d,
1 H, J(gem ) = 11.9 (CH2Ph ); 4.44–4.32 m , 4 H (CH2Ph ); 4.12 dd, 1 H, J(6,7) = J(6,7′) = 6.0
(H-6); 4.08 dd, 1 H, J(3,4) = 4.1 (H-3); 3.82–3.78 m , 2 H (H-4, H-5); 3.58–3.46 m , 2 H (H-7′,
H-7); 3.09 s, 1 H (OH). 13C NMR: 138.23, 138.17, 138.12, 138.01 (quatern ary C-arom );
135.70 (C-2); 128.26–127.51 (CH-arom ); 119.08 (C-1); 82.13 (C-4 or C-5); 80.75 (C-3); 76.63
(C-4 or C-5); 75.16, 73.11 (2 × CH2Ph ); 73.06 (C-7); 71.17, 70.30 (2 × CH2Ph ); 69.67 (C-6).
For C35H38O5 (538.7) calculated: 78.04% C, 7.11% H; foun d: 77.82.25% C, 6.98% H.
Th en th e elim in ation product (2R,3S,4E)-1,3,5-tris(ben zyloxy)h epta-4,6-dien -2-ol (16) was
isolated (0.16 g, 0.3 m m ol, 15%), [α]D –5.8 (c 0.5, CHCl3). 1H NMR (500 MHz, CDCl3):
7.36–7.26 m , 15 H (H-arom ); 6.24 dd, 1 H (H-6); 5.58 d, 1 H, J(7′,6) = 17.4 (H-7′); 5.28 d,
1 H, J(7,6) = 10.9 (H-7); 5.12 d, 1 H, J(4,3) = 9.7 (H-4); 4.78 d, 1 H, J(gem ) = 11.3 (CH2Ph );
4.74 d, 1 H, J(gem ) = 11.3 (CH2Ph ); 4.54–4.48 m , 3 H (CH2Ph ); 4.42 dd, 1 H, J(3,2) = 6.0
(H-3); 4.27 d, 1 H, J(gem ) = 11.7 (CH2Ph ); 3.73–3.69 m , 1 H (H-2); 3.51–3.45 m , 2 H (H-1′,
H-1); 2.72 s, 1 H (OH). 13C NMR: 156.79 (C-5); 138.34, 138.12, 137.10 (quatern ary C-arom );
131.84 (C-6); 128.50–127.51 (CH-arom ); 116.46 (C-7); 115.10 (C-4); 73.47 (CH2Ph ); 73.43
(C-3); 73.40 (CH2Ph ); 73.28 (C-2); 70.99 (C-1); 70.25 (CH2Ph ). For C28H30O4 (430.6) calcu-
lated: 78.11% C, 7.02% H; foun d: 77.95% C, 7.22% H.
Method B. Usin g MePh 3PBr (6.18 g, 17.3 m m ol) in THF (45 m l), butyllith ium (1.6 M in
h exan e, 13 m l, 20.8 m m ol) an d a solution of 2,3,4,6-tetra-O-ben zyl-D-galactopyran ose (3.32 g,
Collect. Czech. Chem. Commun. 2006, Vol. 71, Nos. 11–12, pp. 1659–1672