PALLADIUM-CATALYZED P-ARYLATION OF HYDROPHOSPHORYL DERIVATIVES
1783
Yield 0.49 g (31%), colorless oily substance, Rf 0.60
(B). 13C NMR spectrum (CDCl3), δC, ppm: 15.4 s,
15.5 s (OCH2CH3); 24.4–26.2 s [C(CH3)2]; 61.2 d,
1.1 equiv of phenylphosphonous dichloride in 3 ml of
dioxane at a bath temperature of 12°C. The mixture
was stirred for 30 min at room temperature and cooled,
and a solution of 1.1 equiv of water in 3 ml of dioxane
was slowly added dropwise. The mixture was stirred
for 30 min at room temperature and left overnight, the
precipitate of pyridine hydrochloride was filtered off,
the filtrate was evaporated, and the residue was sub-
jected to column chromatography on silica gel.
2
61.4 d (OCH2CH3, JPC = 6.5, 7.6 Hz); 66.3 s (C6);
2
71.3 s, 71.6 s (C5); 77.6 d (C3, JPC = 4.8 Hz); 79.6 d,
3
3
79.7 d (C4, JPC = 5.0 Hz); 83.0 d, 83.2 d (C2, JPC
=
9.7 Hz); 104.4 s, 104.6 s (C1); 108.0 s, 110.6 s, 108.6 s
[C(CH3)2]. 31P NMR spectrum (CHCl3), δP, ppm: 7.4 d
(1JPH = 715.8 Hz), 8.3 d (1JPH = 715.8 Hz). Calculated,
%: C 47.73; H 7.15; P 8.79. C14H25O8P. Found, %:
C 47.49; H 7.05; P 8.61.
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-phenylphosphinate (XI) was synthesized from
0.80 g of phenylphosphonous dichloride, 1.06 g of
monosaccharide I, 0.81 g of pyridine, and 0.08 g of
water. The product was purified by chromatography on
silica gel L (100–160 μm) using solvent system A as
eluent. Yield 0.67 g (43%), colorless powder, mp 115–
117°C, Rf 0.51 (A). 13C NMR spectrum (CDCl3), δC,
ppm: 24.9–26.5 s [C(CH3)2]; 67.0 s, 67.4 s (C6); 72.4 s
(C5); 74.0 s, 74.6 s (C3); 81.1 s, 83.4 s (C4); 83.5 s,
84.9 s (C2); 104.8 s, 105.0 s (C1); 108.9 s, 111.3 s,
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(butyl phosphonate) (IX) was synthesized from
0.75 g of butyl phosphorodichloridite, 1.01 g of com-
pound I, 0.77 g of pyridine, and 0.08 g of water. The
product was purified by chromatography on silica gel
L (100–160 μm) using solvent system E as eluent.
Yield 0.52 g (35%), colorless oily substance, Rf 0.16
(E). 13C NMR spectrum (CDCl3), δC, ppm: 12.6 s
(CH2CH3); 17.7 s (CH2CH2CH3); 24.2–25.9 s
[C(CH3)2]; 31.4 s (OCH2CH2); 64.7 d (OCH2CH2,
2JPC = 7.5 Hz); 66.3 s, 66.4 s (C6); 71.2 s, 71.5 s (C3);
109.2 s, 112.2 s [C(CH3)2]; 128.4 s, 128.7 s (C3');
1
130.6 s (C2'); 131.3 s (C4'); 131.9 d (C1′, JPC
=
3
3
77.2 s (C5); 79.5 d, 79.6 d (C4, JPC = 5.6, JPC
=
153.0 Hz). 31P NMR spectrum (CHCl3), δP, ppm:
28.2 d (1JPH = 578.0 Hz), 26.5 d (1JPH = 577.3 Hz).
Found, %: C 56.15; H 6.66; P 7.98. C18H25O7P. Cal-
culated, %: C 56.25; H 6.56; P 8.06.
5.1 Hz); 82.9 d (C2, JPC = 9.9 Hz); 104.3 s (C1);
3
108.3 s, 111.2 s [C(CH3)2]. 31P NMR spectrum (C6H6),
δP, ppm: 8.1 d (1JPH = 717.6 Hz), 7.2 d (1JPH
=
728.8 Hz). Found, %: C 50.43; H 7.77; P 8.10.
C16H29O8P. Calculated, %: C 50.52; H 7.68; P 8.14.
Methyl 2,3-O-isopropylidene-α-L-ramnopyrano-
side 4-phenylphosphinate (XIII) was synthesized
from 0.59 g of phenylphosphonous dichloride, 0.65 g
of monosaccharide II, 0.59 g of pyridine, and 0.06 g of
water. The product was purified by chromatography on
silica gel L (100–160 μm) using solvent system C as
eluent. Yield 0.28 g (27%), Colorless oily substance,
Rf 0.32 (C). 13C NMR spectrum (CDCl3), δC, ppm:
18.2 s (C6); 26.5–28.7 s [C(CH3)2]; 54.8 s (OCH3);
63.9 s, 64.0 s (C5); 75.9 s, 76.0 s (C2); 78.3, 78.6 s
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(cyclohexyl phosphonate) (X) was synthesized
from 0.86 g of cyclohexyl phosphorodichloridite,
1.02 g of compound I, 0.77 g of pyridine, and 0.08 g of
water. The product was purified by chromatography on
silica gel L (100–160 μm) using solvent system D as
eluent. Yield 0.47 g (30%), colorless oily substance,
Rf 0.40 (D). 13C NMR spectrum (CCl4–CDCl3), δC,
ppm: 22.8 s, 23.5 s (C3'); 25.3–25.4 s [C(CH3)2];
26.5 s, 27.0 s (C4'); 31.7 s, 33.7 s (C2'); 67.4 s (C6);
2
(C3); 79.1 d (C4, JPC = 7.2 Hz); 97.7 s (C1); 109.5 s,
2
110.0 s [C(CH3)2]; 128.5 d, 128.8 d (C2', JPC = 7.1,
2
72.2 s, 72.5 s (C5); 75.4 d (C3, JPC = 4.5 Hz); 77.9 d
7.0 Hz); 130.5 s, 130.8 s (C3'); 131.0 s, 131.3 s (C4');
(C1', 2JPC = 4.3 Hz); 80.6 d, 80.7 d (C4, 3JPC = 5.1 Hz);
1
132.2 d (C1', JPC = 93.4 Hz). 31P NMR spectrum
3
84.0 d (C2, JPC = 12.0 Hz); 105.2 s, 105.3 s (C1);
(CHCl3), δP, ppm: 26.6 d, 27.1 d (1JPH = 572.3 Hz).
Found, %: C 56.25; P 8.93. C16H23O6P. Calculated, %:
C 56.14; P 9.05.
31
109.1 s, 111.9 s, 109.2 s, 112.0 s [C(CH3)2]. P NMR
spectrum (CH2Cl2), δP, ppm: 6.7 d (1JPH = 705.1 Hz),
5.5 d (1JPH = 708.7 Hz). Calculated, %: C 53.20;
H 7.69; P 7.62. C18H31O8P. Found, %: C 53.02; H 7.49;
P 7.52.
Diglycosyl phosphonates XIV and XV (general
procedure). Monosaccharide I or II, 2 equiv, was dis-
solved in 3 ml of dioxane, 1.3 equiv of phosphonic bis-
(dimethylamide) was added, and the mixture was
heated for 6 h at a bath (glycerol) temperature of 60°C.
The solvent was evaporated, and the residue was
purified by column chromatography.
Phenylphosphinates XI and XIII (general proce-
dure). A solution of 1 equiv of monosaccharide I or II
and 2.5 equiv of pyridine in 5 ml of dioxane was added
dropwise over a period of 20–30 min to a solution of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006