Palladium-catalyzed P-arylation of hydrophosphoryl derivatives of protected monosaccharides

Article abstract of DOI:10.1134/S1070428006120049

Palladium-catalyzed arylation of hydrophosphorylated protected monosaccharides of the pyranose and furanose series gave the corresponding P-aryl derivatives.

Full text of DOI:10.1134/S1070428006120049

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 12, pp. 1780–1785. © Pleiades Publishing, Inc., 2006.
Original Russian Text © I.P. Beletskaya, N.B. Karlstedt, E.E. Nifant’ev, D.V. Khodarev, T.S. Kukhareva, A.V. Nikolaev, A.J. Ross, 2006, published in
Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 12, pp. 1793–1797.
Palladium-Catalyzed P-Arylation of Hydrophosphoryl
Derivatives of Protected Monosaccharides
I. P. Beletskayaa, N. B. Karlstedta, E. E. Nifant’evb, D. V. Khodarevb, T. S. Kukharevab,
A. V. Nikolaevc, and A. J. Rossc
a Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: beletska@org.chem.msu.ru
b Moscow State Pedagogical University, Moscow, Russia
e-mail: chemdept@mtu-net.ru
c Faculty of Life Sciences, University of Dundee, Dundee, Great Britain
e-mail: avnikolaev@dundee.ac.uk
Received May 19, 2006
Abstract—Palladium-catalyzed arylation of hydrophosphorylated protected monosaccharides of the pyranose
and furanose series gave the corresponding P-aryl derivatives.
DOI: 10.1134/S1070428006120049
Palladium-catalyzed arylation and vinylation of
compounds containing a P–H bond with formation of
a new Csp2–P bond have been extensively studied [1].
These reactions include primarily arylation and vinyla-
tion of dialkyl phosphonates [2], and various proce-
dures were proposed to accomplish such processes [3].
Apart from common dialkyl phosphonates, phosphor-
ylated derivatives of thymidine [4] and dinucleoside
[5] were used as substrates. Arylation and vinylation
were also performed under analogous conditions with
alkyl(phenyl)phosphonous acid esters [6] to give aryl-
(vinyl)phosphinates, as well as with phosphinous acid
esters [7] and phosphinous acid itself [8]. Increasing
interest in the synthesis of compounds having a Csp2–P
bond via arylation and vinylation of hydrophosphoryl
compounds in the presence of copper complexes
should also be noted [9].
the pyranose and furanose series having different
phosphorus-containing groups: (SugO)P(OR')(O)H,
(SugO)2P(O)H, and (SugO)PPh(O)H; these groups
turned out to strongly differ in their reactivity. As sub-
strates we used phosphinates and phosphonates derived
from the following accessible monosaccharides:
1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (I),
methyl 2,3-O-isopropylidene-α-L-ramnopyranoside
(II), and benzoylated mannopyranose III.
Phosphorus-containing sugars VIII–XI and XIII
were synthesized in two steps. In the first step, the
substrate was treated with dichlorophosphine. Inter-
mediate P(III) chlorides were detected by 31P NMR
spectroscopy: the spectra contained singlets in the
region δP 168–174 ppm due to compounds IV–VII and
XII. Chlorides IV–VII and XII are very labile, and
they were subjected to controlled hydrolysis by addi-
tion of an equimolar amount of water to the reaction
mixture (Schemes 1, 2). Ethyl 2,3,4,6-tetra-O-benzoyl-
In the present work we examined the arylation of
phosphorylated derivatives of a number of sugars of
Scheme 1.
O
OH
O
O
O
RPCl2, pyridine
dioxane
O
H2O, pyridine
dioxane
O
O
O
O
O
O
Cl
O
O
P
O
P
O
H
O
O
O
R
R
I
IV–VII
VIII–XI
IV, VIII, R = EtO; V, IX, R = BuO; VI, X, R = cyclo-C6H11O; VII, XI, R = Ph.
1780

PALLADIUM-CATALYZED P-ARYLATION OF HYDROPHOSPHORYL DERIVATIVES
1781
Scheme 2.
OMe
OMe
OMe
PhPCl2, pyridine
dioxane
H2O, pyridine
dioxane
O
O
O
HO
O
O
Cl
P
O
P
O
O
O
H
O
O
O
Ph
Ph
II
XII
XIII
Scheme 3.
SugO
O
H
60°C, dioxane
2 Sug–OH
+
(Me2N)P(O)H
P
+
2 Me2NH
SugO
I, II
XIV, XV
α-D-mannopyranosyl phosphonate III was synthesized
by reaction of 2,3,4,6-tetra-O-benzoyl-α-D-mannopyr-
anozyl hydrogen phosphonate with ethanol in the pres-
ence of pivaloyl chloride according to the procedure
described in [10]. Diglycosyl phosphonates XIV and
XV were prepared by phosphorylation of monosac-
charides I and II, respectively, with phosphonic bis-
(dimethylamide) (Scheme 3). Phosphorylated sugars
VIII–XI and XIII–XV were purified by column chro-
matography. Compound III was subjected to arylation
cursor of Pd(0). The arylation readily occurred with
compounds III, VIII–X, and XIII (Schemes 4, 5).
Usually, the reaction was complete in 3 h; however, the
reaction with pyranose derivative XIII required only
1.5 h. Sterically more hindered phosphonate XV
required heating for 5 h at 100°C. The arylation prod-
ucts were formed in ~80% yield (according to the 31P
NMR data), and they were isolated in 60–70% yield by
column chromatography. In all cases, the reactions
were accompanied by partial hydrolysis of the initial
without additional purification. According to the 31P phosphorylated monosaccharides, so that the 31P NMR
and 13C NMR data, compounds III, VIII–XI, and XIII
were approximately equimolar mixtures of two dia-
stereoisomers.
spectra contained signals from the P-arylated hydrol-
ysis products. For example, the 31P NMR spectrum of
the reaction mixture obtained from compound VIII
contained low-intensity signals at δP 28.5 and 3.9 ppm
[EtO(HO)P(O)Ph and EtO(HO)P(O)H, respectively].
Phosphorylated monosaccharide derivatives III,
VIII–XI, and XIII–XV were brought into reaction
with iodobenzene in the presence of zero-valent palla-
dium complex. The reactions were carried out under
conditions of phase-transfer catalysis (K2CO3–
Et3BzlN+ Cl–) at 90–95°C using Pd(PPh3)2Cl2 as pre-
The arylation of butyl glucofuranosyl phosphonate
IX was also performed under conditions of microwave
activation. The application of microwave irradiation to
accelerate organic reactions is well known [11]. This
Scheme 4.
O
O
O
O
PhI, [Pd], K2CO3
dioxane, 95°C
O
O
O
O
O
O
P
O
P
O
H
Ph
O
O
R
R
VIII–X
XVI–XVIII
OMe
OMe
PhI, [Pd], K2CO3
dioxane, 95°C
O
O
O
O
O
P
O
P
R
O
O
H
Ph
O
O
R
XIII, XIV
XIX, XX
VIII, XVI, R = EtO; IX, XVII, R = BuO; X, XVIII, R = cyclo-C6H11O; XIII, XIX, R = Ph; XV, XX, R = SugO.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

BELETSKAYA et al.
1782
Scheme 5.
OBz
OBz
OBz
O
OBz
O
PhI, [Pd], K2CO3
dioxane, 95°C
BzO
BzO
BzO
BzO
O
O
O
O
P
P
OEt
OEt
Ph
H
III
XXI
Scheme 6.
OMe
OMe
O
O
[Pd], Et3N
Br
O
O
dioxane, 95°C
+
O
P
O
P
O
O
H
O
O
Ph
Ph
N
N
XIII
XXII
technique is also used in the chemistry of organo-
phosphorus compounds [12]. We have found that catal-
ysis by Pd(PPh3)2Cl2 in combination with microwave
activation makes it possible to strongly shorten the
reaction time (from 3 h to 14 min).
ment at 32.4 MHz and on a Bruker Avance-400 spec-
trometer at 162 MHz; 85% phosphoric acid was used
as external reference. The mass spectra were obtained
on a Bruker Autoflex II instrument. Silica gel L (100–
160 and 40–60 μm) was used for column chromatog-
raphy. Analysis by thin-layer chromatography was per-
formed on Silufol UV-254 plates using the following
solvent systems: benzene–dioxane, 7:1 (A), 8:1 (B);
hexane–dioxane, 3:1 (C), 5:1 (D), 6:1 (E); petroleum
ether–dioxane, 2:1 (F); spots were visualized by treat-
ment with iodine vapor and by calcination. All syn-
theses were carried out in pure dehydrated solvents
under dry oxygen-free argon.
Glucofuranosyl derivatives XI and XIV turned out
to be considerably less stable than their pyranose ana-
logs XIII and XV; their arylation resulted in formation
of a mixture of phosphorus-containing products.
Unexpected results were obtained while attempting
to effect arylation with different bromopyridines. The
reactions were carried out in the presence of Pd(PPh3)4
using triethylamine as a base. In all cases, except for
the reaction with compound XIII, the desired P-aryla-
tion products were formed in an amount of 3–5%,
while the main process was reduction of bromopyri-
dine and formation of (SugO)P(OR')(O)Br (up to 62%,
according to the 31P NMR data). By reaction of XIII
with 3-bromopyridine at 85°C in 50 min we obtained
the corresponding arylation product XXII in almost
quantitative yield (>90%; 31P NMR) (Scheme 6).
Phosphonates VIII–X (general procedure). A solu-
tion of 1 equiv of monosaccharide I and 2.5 equiv of
pyridine in 5 ml of dioxane was added dropwise to
a solution of 1.1 equiv of the corresponding alkyl
phosphorodichloridite in 3 ml of dioxane at a bath
temperature of 12°C. The mixture was stirred for
30 min at room temperature, cooled, and a solution of
1.1 equiv of water in 3 ml of dioxane was slowly
added in a dropwise manner. 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.
On the other hand, compound XIII almost failed to
react with other hetaryl bromides; in the reaction with
2-bromothiophene, the conversion of XIII was as low
as 3% in 6 h at 95–100°C, and decomposition of XIII
was observed.
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(ethyl phosphonate) (VIII) was synthesized from
0.66 g of ethyl phosphorodichloridite, 1.06 g of mono-
saccharide 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 B as eluent.
EXPERIMENTAL
The 13C NMR spectra were measured on a Bruker
AC-200 spectrometer at 50.32 MHz. The 31P NMR
spectra were recorded on a Bruker WP-80SY instru-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

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

BELETSKAYA et al.
1784
6 ml), the solvent was distilled off from the filtrate
under reduced pressure, and the oily residue was
subjected to column chromatography on silica gel L
(40–60 μm).
Bis(1,2:5,6-di-O-isopropylidene-α-D-glucofura-
nose) 3,3'-phosphonate (XIV) was synthesized from
0.94 g of 1,2:5,6-di-O-isopropylidene-α-D-glucofura-
nose and 0.32 g of phosphonic bis(dimethylamide).
The product was purified by chromatography on silica
gel L (100–160 μm) using solvent system F as eluent.
Yield 0.25 g (12%), colorless oily substance, Rf 0.41
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(ethyl phenylphosphonate) (XVI) was synthesized
from 0.09 g of compound VIII. The product was
purified by chromatography using solvent system F as
eluent. Yield 0.055 g (55%), colorless oily substance,
Rf 0.5 (F). 31P NMR spectrum (dioxane), δP, ppm:
17.9, 19.5. Found, %: P 7.44 C20H29O8P. Calculated,
%: P 7.23.
1
(F). H NMR spectrum (C6D6), δ, ppm: 1.05–1.34 s
[24H, C(CH3)2], 4.0 m (4H, 4-H, 6'-H), 4.3 m (4H,
3
5-H, 6-H), 4.8 d.d (2H, 2-H, J2,1 = 3.4 Hz), 5.2 d (2H,
3
3
3-H, JHP = 10.1 Hz), 5.8 d and 5.9 d (2H, J1,2
=
3.4 Hz), 7.0 d (1H, PH, JPH = 721.1 Hz). 31P NMR
1
spectrum (C6H6): δP 7.1 ppm, d.d (1JPH = 721.1, 3JPH
=
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(butyl phenylphosphonate) (XVII). a. Compound
XVII was synthesized from 0.1 g of phosphonate IX.
The product was purified by chromatography using
solvent system B as eluent. Yield 0.128 g (64%),
colorless oily substance.
10.1 Hz). Found, %: C 50.30; H 7.05; P 4.91.
C24H39O13P. Calculated, %: C 50.88; H 6.94; P 5.47.
Bis(methyl 2,3-O-isopropylidene-α-L-ramno-
pyranoside) 4,4'-phosphonate (XV) was synthesized
from 1.11 g of methyl 2,3-O-isopropylidene-α-L-
ramnopyranoside and 0.44 g of phosphonic bis(di-
methylamide). The product was purified by chroma-
tography on silica gel L (100–160 μm) using solvent
system D as eluent. Yield 0.60 g (24%), colorless oily
b. The cross coupling with iodobenzene was carried
out in a microwave furnace (2450 MHz, 290 W). The
reaction was complete in 14 min. Yield 0.13 g (66%),
Rf 0.51 (B). 31P NMR spectrum (dioxane), δP, ppm:
17.9, 19.6. Found, %: P 6.60. C22H33O8P. Calculated,
%: P 6.79.
1
substance, Rf 0.37 (D). H NMR spectrum (C6D6), δ,
ppm: 1.2 s (6H, C6H3), 1.4–1.6 s [12H, C(CH3)2],
3.03 s and 3.05 s (3H each, OCH3), 3.7 m (2H, 4-H),
3
3
4.1 d.d (2H, 3-H, J3,32 = 5.5, J3,4 = 4.3 Hz), 4.2 d.d
1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose
3-(cyclohexyl phenylphosphonate) (XVIII) was syn-
thesized from 0.11 g of compound X. The product was
purified by chromatography using solvent system B as
eluent. Yield 0.07 g (62%), colorless oily substance,
Rf 0.56 (B). 31P NMR spectrum (dioxane), δP, ppm:
16.5, 17.9. Found, %: P 6.29. C24H35O8P. Calculated,
%: P 6.42.
3
(2H, 2-H, J2,1 = 6.1, J2,3 = 5.5 Hz), 4.4 m (2H, 4-H,
2JHP = 10.5, 3J4,5 = 7.3, 3J4,3 = 4.3 Hz), 4.8 d (2H, 1-H,
1
3J1, 2 = 6.1 Hz), 7.4 d (1H, PH, JPH = 713.8 Hz).
31P NMR spectrum (C6H6): δP 7.1 ppm, d.d (1JPH
713.8, JPH = 10.5 Hz). Found, %: C 51.0; H 7.54;
P 6.91. C20H35O11P. Calculated, %: C 49.79; H 7.31;
P 6.42.
=
3
Palladium-catalyzed arylation of phosphorylated
sugars with iodobenzene. An ampule was evacuated,
filled with argon, and charged with a solution of
0.26 mmol of compound III, VIII–X, XIII, or XV in
0.5 ml of dioxane, and 0.04 g (0.29 mmol) of calcined
K2CO3, 0.004 g (2 mmol %) of Pd(PPh3)2Cl2, 0.006 g
(0.025 mmol) of benzyltriethylammonium chloride,
and 0.051 g (0.25 mmol) of iodobenzene were added
in succession. The ampule was sealed, and the mixture
was stirred and heated at 90–95°C with intermittent
shaking. The ampule was then opened, 1 ml of water
and 5 ml of chloroform were added to the mixture, the
mixture was stirred, and the aqueous phase was
separated and extracted with chloroform. The extracts
were combined with the organic phase, dried over
calcined Na2SO4, and filtered through a thin (~3 mm)
layer of silica gel on a glass filter (to remove palladium
black), the sorbent was washed with chloroform (2×
Methyl 2,3-O-isopropylidene-α-L-ramnopyrano-
side 4-diphenylphosphinate (XIX) was synthesized
from 0.09 g of compound XIII. The reaction mixture
was heated for 1.5 h at 90–95°C, and the product was
purified by chromatography using solvent system F as
eluent. Yield 0.073 g (67%), colorless oily substance,
Rf 0.51 (F). 31P NMR spectrum (dioxane): δP 31.3 ppm.
Found, %: P 7.15. C22H27O6P. Calculated, %: P 7.40.
Bis(methyl 2,3-O-isopropylidene-α-L-ramno-
pyranoside 4,4'-phenylphosphonate (XX) was syn-
thesized from 0.12 g of compound XV. The reaction
mixture was heated for 5 h at 100°C, and the product
was purified by chromatography on silica gel L
(100–160 μm) using solvent system D as eluent. Yield
0.076 g (58%), Rf 0.42 (D). 31P NMR spectrum (di-
oxane): δP 17.74 ppm. Found, %: P 5.16. C26H39O11P.
Calculated, %: P 5.54.
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PALLADIUM-CATALYZED P-ARYLATION OF HYDROPHOSPHORYL DERIVATIVES
1785
Comprehensive Coordination Chemistry II: from
Biology to Nanotechnology, McCleverty, J.A. and
Meyer, T.J., Eds., Amsterdam: Elsevier, 2004, p. 386.
2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranose
1-(ethyl phenylphosphonate) (XXI) was synthesized
from 0.14 g (0.2 mmol) of compound III (31P NMR
spectrum of III in CDCl3: δP 6.13, 6.85 ppm). The
product was purified by chromatography on silica
gel L (40–60 μm) using petroleum ether–ethyl acetate
(5:2) as eluent (development with UV light). Yield
0.094 g (63%), Rf 0.15 (petroleum ether–ethyl acetate,
5:2). 31P NMR spectrum (dioxane), δP, ppm: 16.9, 17.2.
Mass spectrum (MALDI-TOF, anthracene matrix):
m/z: 803 [M + K]+.
2. Hirao, T., Masunaga, T., Ohshiro, Y., and Agawa, T.,
Synthesis, 1981, p. 56; Hirao, T., Masunaga, T., Yama-
da, N., Ohshiro, Y., and Agawa, T., Bull. Chem. Soc.
Jpn., 1982, vol. 55, p. 909.
3. Kabachnik, M.M., Solntseva, M.D., Izmer, V.V., Novi-
kova, Z.S., and Beletskaya, I.P., Russ. J. Org. Chem.,
1998, vol. 34, p. 93; Goossen, L.J. and Dezfuli, M.K.,
Synlett, 2005, p. 445.
4. Abbas, S. and Hayes, Ch.I., Synlett, 1999, p. 1124;
Abbas, S. and Hayes, Ch.I., Tetrahedron Lett., 2000,
vol. 41, p. 4513.
Methyl 2,3-O-isopropylidene-α-L-ramnopyrano-
side 4-phenyl(3-pyridyl)phosphinate (XXII). A mix-
ture of 0.1 g (0.26 mmol) of compound XIII, 0.6 ml of
dry oxygen-free dioxane, 0.036 ml (0.26 mmol) of
triethylamine, 0.04 g (0.25 mmol) of 3-bromopyridine,
and 0.014 g (5 mol %) of Pd(PPh3)4 was heated for
50 min at 85°C. The mixture was then diluted with
6 ml of anhydrous petroleum ether, the precipitate was
filtered off, the solvent was distilled off from the
filtrate, and the oily residue was subjected to column
chromatography on silica gel (100–160 μm) using
benzene–dioxane, 8:2 as eluent. Yield 0.077 g (68%),
partially crystallizing oily substance, Rf 0.35. 31P NMR
spectrum (CDCl3), δP, ppm: 29.32, 31.65. Mass spec-
trum: m/z 458 [M + K]+.
5. Johansson, T. and Stawinski, J., Chem. Commun., 2001,
p. 2564.
6. Xu, Y., Li, Z., and Xia, J., Synthesis, 1983, p. 377;
Xu, Y. and Zhang, J., Synthesis, 1984, p. 778; Xu, Y. and
Li, Z., Synthesis, 1986, p. 240.
7. Schwabacher, A.W. and Stefanescu, A.D., Tetrahedron
Lett., 1996, vol. 37, p. 425.
8. Montschamp, J.L. and Dumond, Y.R., J. Am. Chem.
Soc., 2001, vol. 123, p. 510.
9. Gelman, D., Jiang, L., and Buchwald, S.L., Org. Lett.,
2003, p. 2315; Beletskaya, I.P. and Cheprakov, A.V.,
Coord. Chem. Rev., 2004, vol. 248, p. 2337.
10. Nikolaev, A.V., Ivanova, I.A., Shibaev, V.N., and Ko-
chetkov, N.K., Carbohydr. Res., 1990, vol. 204, p. 65.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006