Synthesis of S-glycosyl thiophosphates, thiophosphonates and thiophosphinates by the Michaelis-Arbuzov rearrangement of anomeric thiocyanates

Article abstract of DOI:10.1016/j.carres.2007.12.009

Reaction of anomeric thiocyanates with a series of O-alkyl or O-trimethylsilyl phosphite, phenylphosphonite and diphenylphosphinite derivatives afforded the corresponding S-glycosyl thiophosphates, thiophosphonates and thiophosphinates in good yields. These derivatives had been previously applied as glycosyl donors in the synthesis of benzyl glycosides and disaccharides with excellent stereoselectivity.

Full text of DOI:10.1016/j.carres.2007.12.009

Available online at www.sciencedirect.com
Carbohydrate Research 343 (2008) 785–792
Note
Synthesis of S-glycosyl thiophosphates, thiophosphonates and
thiophosphinates by the Michaelis–Arbuzov rearrangement of
anomeric thiocyanates
Marta Piekutowska and Zbigniew Pakulski*
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland
Received 5 November 2007; received in revised form 7 December 2007; accepted 12 December 2007
Available online 23 December 2007
Abstract—Reaction of anomeric thiocyanates with a series of O-alkyl or O-trimethylsilyl phosphite, phenylphosphonite and diphenyl-
phosphinite derivatives afforded the corresponding S-glycosyl thiophosphates, thiophosphonates and thiophosphinates in good
yields. These derivatives had been previously applied as glycosyl donors in the synthesis of benzyl glycosides and disaccharides with
excellent stereoselectivity.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: Thiocyanates; Thiophosphates; Thiophosphonates; Thiophosphinates; Glycosyl donors
The effectiveness of glycosylation is a key problem in
oligosaccharide synthesis and strongly depends upon
the nature of the leaving group at the anomeric centre
and its method of activation. Numerous versatile leaving
groups are known;1 however, a universally applicable
method for glycoside bond formation is not available.
Therefore, the need for new, readily accessible, stable
and reactive glycosyl donors still persists. During our
studies directed towards the synthesis of oligosaccha-
rides2 we focused our attention on the leaving groups
containing a phosphorus–sulfur bond. Recently, we
reported that S-glycosyl thiophosphates, thiophos-
phonates and thiophosphinates are very promising
glycosyl donors and give glycosides and disaccharides
with excellent stereoselectivity.3 Numerous synthetic
methods for the introduction of a phosphorothioate
moiety into a saccharide structure have been reported4
but they often lead to a mixture of anomers or O,S-
isomerisation. S-Glycosyl thiophosphates have also
been used in the synthesis of glycosyl cyanides and
glycosyl 1-O-acyl esters,5 S-glycosyl thiophosphonates
for studies of phosphorus stereochemistry,6 whereas
S-glycosyl thiophosphinates have not been described
yet.
The Michaelis–Arbuzov reaction (also known as the
Arbuzov reaction or Arbuzov rearrangement) is well
known and widely used in general organic chemistry
for the creation of carbon–phosphorus bonds.7 It has
also been demonstrated that alkyl and aryl thiocyanates
are highly reactive reagents in this reaction.8 The reac-
tion involves S–CN bond fission and gives alkyl cya-
nates and O,O,S-trialkyl thiophosphates (Scheme 1).
R1R2P+ SR3
R1R2P OR
R3SCN
R1R2P SR3
O
RCN
+
+
O
R
CN-
Scheme 1.
*
Corresponding author. Fax: +48 22 632 66 81; e-mail: pakul@icho.edu.pl
0008-6215/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2007.12.009

786
M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
Therefore, organic thiocyanates are potentially very
promising substrates for the highly regioselective prepa-
ration of unsymmetrical O,O,S-trialkyl thiophosphates.9
In this regard, anomeric thiocyanates10,11 are particu-
larly interesting starting materials for the preparation
of anomeric thiophosphorus derivatives.
In this paper, we report a highly efficient method for
the preparation of S-glycosyl thiophosphates, thio-
phosphonates and thiophosphinates via Michaelis–
Arbuzov reaction of glycosyl thiocyanates with simple
phosphorus reagents.
glycosyl thiosphosphates 6, 7 and 9, 10 in moderate
yields; the results are summarised in Table 1.
Based on the 31P NMR data, the purity of thiophos-
phates 5–7 obtained by the treatment of thiocyanates
1–3 with triethylphosphite fluctuated between 77% and
99% and the products were contaminated with
H2P(O)(OEt), HP(O)(OEt)2 and HOP(O)(OEt)2. The
purities of compounds 8–10 obtained by the treatment
of thiocyanates 1–3 with tributylphosphite were only
30–46%; byproducts including HP(O)(OBu)2 and HO-
P(O)(OBu)2 were formed.3
As we described earlier,3 peracetylated glycosyl thio-
cyanates are thermally unstable and at high temperature
(usually required for the Arbuzov reaction) easily iso-
merise to the corresponding glycosyl isothiocyanates.
We decided, therefore, to use the much more thermally
stable perbenzoylated glycosyl thiocyanates 1–4
(Fig. 1) as the starting materials. These compounds are
readily available by the treatment of the corresponding
glycosyl bromides with potassium thiocyanate in the
presence of 18-crown-6,10 or by a slightly modified
method in which the relatively expensive crown ether
is replaced by 1-butyl-3-methylimidazolium chloride
([bmim]Cl) without decreasing the yields.
Unsatisfying reaction yields and contamination of the
desired products with inseparable compounds prompted
us to search for more efficient organophosphorus
reagents. A known method of activation of the phosho-
rus(III) acids is their conversion into the trimethylsilyl-
oxy derivatives.13 This approach was successful; we
have found that the reaction of thiocyanates 1–3 with
diethyltrimethylsilylphosphite [(EtO)2P–OTMS] pro-
ceeded smoothly at slightly elevated temperature (even
room temperature) and afforded (after simple chromato-
graphic separation) pure S-glycosyl thiophosphates 5–7
in very good yields (Table 1).
Application of dimethylphenylphosphonite [PhP-
(OMe)2] (instead of triethylphosphite) in the reaction
with glycosyl thiocyanates 1–3 under similar conditions
afforded the expected S-glycosyl thiophosphonates
11–13 (Fig. 1) as an inseparable mixture of diastereo-
isomers and in acceptable yields. The purity of thio-
phosphonates 11–13 varied between 70% and 99%;
HP(O)(Ph)(OMe) and HP(O)(Ph)(OH) were detected
as contaminants by 31P NMR.3
Reaction of 2,3,4,6-tetra-O-benzoyl-D-mannopyrano-
syl bromide with potassium thiocyanate afforded the
known a-D-mannopyranosyl thiocyanate 4, and small
amount of its b-epimer 3 which was not characterised
1
before. The J1H–13C coupling constants of 179.5 Hz
observed at the anomeric carbon atom of 4, and
160.8 Hz of 3 clearly characterise the a- and b-epimers,
respectively.12
Initially, the Michaelis–Arbuzov reaction with the
tetra-O-benzoyl-D-glucose-derived thiocyanate 1 was
carried out in neat triethylphosphite [P(OEt)3] at various
temperatures and afforded the expected thiophosphate 5
(Fig. 1). The highest yield of thiophosphate 5 (51%) was
obtained at 120 °C. Similar reaction with tributyl-
phosphite afforded thiophosphate 8. The same reactions
performed on galactopyranosyl thiocyanate 2 and b-
mannopyranosyl thiocyanate 3 afforded the expected
Again, the use of silylated phenylphosphonite—ethyl-
trimethylsilylphenylphosphonite14 [PhP(OEt)(OTMS)]—
instead of dimethylphenylphosphonite in the reaction
with glycosyl thiocyanates 1–3 gave S-glycosyl thi-
ophosphonates 14–16 in much higher yield, and the
products were completely free from any undesirable
byproducts (Table 1).
Extension of these reaction conditions to methyl di-
phenylphosphinite [Ph2P(OMe)] as a starting material
BzO
BzO
BzO
OBz
O
OBz
O
BzO
BzO
BzO
BzO
BzO
BzO
O
O
BzO
BzO
SCN
SCN
SCN
BzO
BzO
BzO
SCN
BzO
1
2
3
4
BzO
BzO
BzO
BzO
BzO
OBz
O
OBz
BzO
BzO
BzO
BzO
BzO
BzO
O
O
O
O
O
Bz
BzO
BzO
SPR1R2
O
SPR1R2
O
SPR1R2
O
7: R1 = R2 = OEt
10: R1 = R2 = OBu
13: R1 = OMe, R2 = Ph
16: R1 = OEt, R2 = Ph
19: R1 = R2 = Ph
BzO
SPR1R2
O
20: R1 = R2 = OEt
21: R1 = OEt, R2 = Ph
22: R1 = R2 = Ph
SH
BzO
BzO
5: R1 = R2 = OEt
6: R1 = R2 = OEt
23
8: R1 = R2 = OBu
9: R1 = R2 = OBu
11: R1 = OMe, R2 = Ph
14: R1 = OEt, R2 = Ph
17: R1 = R2 = Ph
12: R1 = OMe, R2 = Ph
15: R1 = OEt, R2 = Ph
18: R1 = R2 = Ph
Figure 1.

M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
Table 1. The Michaelis–Arbuzov rearrangement of glycosyl thiocyanates 1–4
787
RSCN
R2P(OR0)
Product
Tempa (°C)
Time
Isolated yield (%)
P(OEt)3
5
5
120
rt
50
120
40
rt
40
40
80
rt
30 min
24 h
1 h
30 min
30 min
18 h
51b
70
(EtO)2P–OTMS
(EtO)2P–OTMS
P(OBu)3
5
82
8
33b
51b
90
OBz
O
PhP(OMe)2
11
14
14
17
17
17
17
PhP(OEt)(OTMS)
PhP(OEt)(OTMS)
Ph2P(OMe)
Ph2P(OMe)
Ph2P(OTMS)
Ph2P(OTMS)
SCN
BzO
BzO
1 h
94
BzO
30 min
10 min
18 h
20b
25b
80
1
40
1 h
71
P(OEt)3
6
6
80
rt
60
80
40
rt
40
rt
40
rt
2 h
24 h
2 h
30b
68
(EtO)2P–OTMS
(EtO)2P–OTMS
P(OBu)3
6
77
9
8 h
30b
53b
85
BzO
BzO
OBz
PhP(OMe)2
12
15
15
18
18
18
18
30 min
18 h
1 h
24 h
30 min
18 h
1 h
O
PhP(OEt)(OTMS)
PhP(OEt)(OTMS)
Ph2P(OMe)
Ph2P(OMe)
Ph2P(OTMS)
Ph2P(OTMS)
SCN
83
BzO
20b
25b
74
2
40
71
P(OEt)3
7
7
80
rt
40
120
50
rt
40
rt
40
3.5 h
24 h
3 h
30 min
1 h
24 h
90 min
24 h
90 min
24b
68
(EtO)2P–OTMS
(EtO)2P–OTMS
P(OBu)3
7
68
40b
41b
85
BzO
10
13
16
16
19
19
BzO
O
PhP(OMe)2
SCN
BzO
BzO
PhP(OEt)(OTMS)
PhP(OEt)(OTMS)
Ph2P(OTMS)
Ph2P(OTMS)
3
89
82
66
(EtO)2P–OTMS
(EtO)2P–OTMS
(EtO)2P–OTMS
PhP(OEt)(OTMS)
PhP(OEt)(OTMS)
PhP(OEt)(OTMS)
Ph2P(OTMS)
20
20
20
21
21
21
22
rt
24 h
24 h
4 h
24 h
24 h
4 h
35
62
53
42
51
33
20c
60
100
rt
60
100
60
BzO
BzO
O
BzO
BzO
SCN
4
24 h
a Bath temperature.
b Purity determined by 31P NMR spectroscopy and the yield was calculated for pure product.
c Product decomposed during chromatographic purification; contains significant amount of thiol 23. Pure thiol 23 (50%) was also isolated.
led to S-glycosyl thiophosphinates 17 and 18 (Fig. 1), but
in very low yields. Thiocyanate 3 was unreactive under
these reaction conditions. In this case, due to the instabil-
ity of the final products at higher temperatures, the reac-
tions were conducted below 80 °C. Because of their high
polarity, chromatographic separation of S-glycosyl
thiophosphinates 17 and 18 was relatively simple and
purities of the products usually exceeded 95%; Ph2P-
(O)(OMe), Ph2P(OH) and H2P(O)(OMe) were detected
as side products by 31P NMR.3 In contrast to the above
reaction, the use of trimethylsilyldiphenylphosphinite15
[Ph2P(OTMS)] afforded S-glycosyl thiophosphinates
17–19 in excellent yield. All products were pure and free
from any contaminants (Table 1).
observed previously, a-D-mannopyranosyl thiocyanate 4
was completely unreactive towards Grignard reagents.10
This compound also remained unchanged during the
Michaelis–Arbuzov rearrangement, and we did not
observe any reaction with triethylphosphite, dimethyl-
phenylphosphonite or methyldiphenylphosphinite. The
reason for the lack of reactivity of a-D-mannopyranosyl
thiocyanate 4 remains unknown. However, when the
more active silylated phosphorus(III) acid derivatives
were used, the Michaelis–Arbuzov reaction took place.
Although the required reaction temperature was higher
and the yields were usually lower than for the corres-
ponding b-D-manno isomer, S-glycosyl thiophosphate
20 and S-glycosyl thiophosphonate 21 were isolated in
good yield (Fig. 1, Table 1). Reaction of thiocyanate 4
with trimethylsilyldiphenylphosphinite afforded S-glycosyl
The unique chemical properties of a-D-mannopyran-
osyl thiocyanate 4 should be mentioned here. As we had

788
M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
thiophosphinate 22, which was confirmed by 31P NMR
spectra of the crude reaction mixture (in which a suit-
able signal at 40.6 ppm was observed). This compound
was, however, unstable and almost complete decomposi-
tion of 22 occurred during flash chromatography and
yielded several decomposition products from which only
thiol 2316 (obtained in 50% yield) could be identified. A
small amount (20%) of the desired product 22 was also
isolated but contaminated with a significant amount of
23. We suppose that thiol 23 was obtained by the hydro-
lysis of S-glycosyl thiophosphinate 22 in the presence of
residual water on silica. This process may be considered
as similar to the known transesterification reaction of
simple alkyl and aryl thiophosphorus esters leading to
the corresponding thiols.17 It should be noted that traces
of 23 were also detected during chromatographic purifi-
cation of S-glycosyl thiophosphonate 21.
In conclusion, we have developed an efficient synthesis
of S-glycosyl thiophosphates, thiophosphonates and thio-
phosphinates from anomeric thiocyanates by treatment
with diethyltrimethylsilylphosphite, ethyltrimethyl-
silylphenylphosphonite or trimethylsilyldiphenylphos-
phinite, respectively. It should be emphasised that in
all the cases studied, the configuration at the stereogenic
centre connected to the sulfur atom (anomeric position)
was fully preserved. Reactions were also regioselective
affording S-glycosyl derivatives as the only products.
1.2. Typical procedure for the preparation of glycosyl
thiocyanate10
A mixture of glycosyl bromide (10.0 mM), potassium
thiocyanate (30.0 mM) and crown ether (18-crown-6,
300 mg) or [bmim]Cl (350 mg) in acetone (50 mL) was
stirred at room temperature for 7 h, and then filtered
through Celite and concentrated. Column chromatogra-
phy (hexane–EtOAc 20:1?7:3) of the residue gave pure
glycosyl thiocyanates 1–4.
1.2.1. 2,3,4,6-Tetra-O-benzoyl-a-D-mannopyranosyl thio-
cyanate (4) and 2,3,4,6-tetra-O-benzoyl-b-D-mannopyrano-
syl thiocyanate (3). As the first product, 2,3,4,6-tetra-
O-benzoyl-D-mannopyranosyl isothiocyanate (29%) was
eluted, the second fraction comprised 2,3,4,6-tetra-O-
benzoyl-a-D-mannopyranosyl thiocyanate (4, 47%) and
the third fraction contained 2,3,4,6-tetra-O-benzoyl-b-
D-mannopyranosyl thiocyanate (3, 16%).
20
Data for thiocyanate 3: mmax (film): 2164 cmꢀ1; ½aꢁD
1
ꢀ89.2 (c 0.4, CHCl3); H NMR (CDCl3) d: 6.06 (m,
2H, H-2, H-4), 5.66 (m, 2H, H-1, H-3), 4.77 (dd, 1H,
0
0
J6,5 = 2.6, J6,6 = 12.3 Hz, H-6), 4.55 (dd, 1H, J6 ,5
=
4.8 Hz, H-60), 4.30 (m, 1H, H-5); 13C NMR (CDCl3)
d: 166.0 (C@O), 165.4 (C@O), 165.1 (C@O), 165.0
(C@O), 108.8 (SCN), 83.1 (C-1), 77.5, 72.0, 70.3, 65.5,
62.4 (C-6); HRMS-ESI calcd for C35H27NNaO9S
[M+Na]+: 660.1299. Found: 660.1274. Anal. Calcd for
C35H27NO9S: C, 65.92; H, 4.27; N, 2.20; S, 5.03. Found:
C, 65.90; H, 4.37; N, 2.05; S, 5.14.
1. Experimental
1.1. General methods
1.3. Typical procedure for the Michaelis–Arbuzov
rearrangement
TLC was performed on silica gel HF-254 and column
chromatography on silica gel 230–400 mesh (Merck).
A mixture of (EtO)2P–OTMS (3 equiv) and thiocyanate
1 (1 equiv) was heated under an argon atmosphere in a
screw cap tube (for reaction details see Table 1). Column
chromatography of the residue (hexane–EtOAc,
9:1?1:1) afforded S-glycosyl phosphate 5.
1
The H, 13C and 31P NMR spectra were recorded at
303 K with a Varian Mercury 400BB spectrometer
(400 MHz, 100 MHz and 161.9 MHz, respectively).
1
TMS was used as the internal standard for H and 13C
NMR spectra, and H3PO4 as the external standard for
31P NMR spectra. Signals of the aromatic groups ob-
served for typical values were omitted for simplicity.
High-resolution mass spectra (HR-MS) were measured
with a MARINER mass spectrometer. Optical rotations
were measured with a JASCO P-1020 automatic polar-
imeter. IR spectra were recorded on Perkin–Elmer
1640 FT-IR spectrophotometer. Unless otherwise sta-
ted, all products were isolated as a foam. Structural
assignments of the S-glycosyl derivatives prepared
above were based on NMR measurements including
DEPT. All isolated compounds gave 1H and 13C
NMR spectra fully consistent with the indicated struc-
tures. Positions of the 31P NMR signals were in good
conformity with the literature data for the correspond-
ing compounds and were consistent with the expected
structures.18
1.3.1. O,O 0-Diethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-gluco-
20
pyranosyl) thiophosphate (5). ½aꢁD +50.3 (c 0.5,
CHCl3); 1H NMR (CDCl3) d: 5.94 (t, 1H, J3,2
=
J3,4 = 9.5 Hz, H-3), 5.71 (t, 1H, J4,5 = 9.9 Hz, H-4),
5.65 (t, 1H, J2,1 = 10.1 Hz, H-2), 5.42 (dd, 1H, JP,H
=
0
12.5 Hz, H-1), 4.63 (dd, 1H, J6,5 = 2.6; J6,6 = 12.4 Hz,
H-6), 4.47 (dd, 1H, J6 5 = 5.4 Hz, H-60), 4.28 (m, 1H,
0
H-5), 3.89–4.14 (m, 4H, 2 ꢂ CH2), 1.21 (dt, J = 7.1,
JH,P = 0.9 Hz, 3H, CH3), 1.11 (dt, J = 7.1, JH,P
=
0.8 Hz, 3H, CH3); 13C NMR (CDCl3) d: 166.0 (C@O),
165.6 (C@O), 165.1 (C@O), 165.0 (C@O), 83.9 (d,
JC,P = 3.4 Hz, C-1), 76.6 (C-5), 73.8 (C-3), 71.2 (d,
JP,C = 9.5 Hz, C-2), 69.0 (C-4), 64.0 (d, JC,P = 5.2 Hz,
CH2), 63.9 (d, JC,P = 5.2 Hz, CH2), 62.9 (C-6), 15.8
(d, JC,P = 2.6 Hz, CH3), 15.7 (d, JC,P = 2.6 Hz, CH3);
31P NMR (CDCl3) d: 22.6; HRMS-ESI calcd for

M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
789
C38H37NaO12PS [M+Na]+: 771.1636. Found: 771.1640.
Anal. Calcd for C38H37O12PS: C, 60.96; H, 4.98; S, 4.28.
Found: C, 60.97; H, 4.77; S, 4.35.
1.3.5. O,O 0-Dibutyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-gluco-
pyranosyl) thiophosphate (8). 1H NMR (CDCl3) d: 5.93
(t, 1H, J3,2 9.5 = J3,4 = 9.5 Hz, H-3), 5.72 (t, 1H,
J4,5 = 9,8 Hz, H-4), 5.65 (t, 1H, J2,1 = 10.1, H-2), 5.43
(dd, 1H, JH,P = 12.5 Hz, H-1), 4.62 (dd, 1H, J6,5 = 2.8,
1.3.2. O,O0-Diethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-galacto-
20
0
0
pyranosyl) thiophosphate (6). ½aꢁD +108.6 (c 0.5,
J6,6 = 12.3 Hz, H-6), 4.47 (dd, 1H, J6 ,5 = 5.1 Hz,
1
CHCl3); H NMR (CDCl3) d: 6.05 (dd, 1H, J4,3 = 3.4,
H-60), 4.27 (m, 1H, H-5); 13C NMR (CDCl3) d: 166.0
J4,5 <1.0 Hz, H-4), 5.90 (t, 1H, J2,1 = J2,3 = 10.0 Hz,
H-2), 5.68 (dd, 1H, H-3), 5.44 (dd, 1H, JP,H = 13.1 Hz,
(C@O), 165.6 (C@O), 165.1 (C@O), 84.0 (d, JC,P =
3.4 Hz, C-1), 76.6, 73.8, 71.2 (d, JC,P = 10.0 Hz), 62.9
(C-6); 31P NMR (CDCl3) d: 22.8. HRMS-ESI calcd
for C42H45NaO12PS [M+Na]+: 827.2262. Found:
827.2242.
0
H-1), 4.64 (dd, 1H, J6,5 = 6.7, J6,6 = 11.2 Hz, H-6),
4.48 (m, 1H, H-5), 4.40 (dd, 1H, J6 ,5 = 5.6 Hz, H-60),
0
3.89–4.15 (m, 4H, 2 ꢂ CH2), 1.22 (dt, J = 7.1, JH,P
CH3); 13C NMR (CDCl3) d: 165.9 (C@O), 165.5
=
0.9 Hz, 3H, CH3), 1.11 (dt, J = 7.1, JH,P = 0.8 Hz, 3H,
1.3.6. O,O0-Dibutyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-galacto-
pyranosyl) thiophosphate (9). 31P NMR (CDCl3) d:
23.1; HRMS-ESI calcd for C42H45NaO12PS [M+Na]+:
827.2262. Found: 827.2269.
(C@O), 165.3 (C@O), 165.2 (C@O), 84.4 (d, JC,P
=
4.3 Hz, C-1), 75.7, 72.4, 68.8 (d, JC,P = 9.5 Hz), 68.3,
63.9 (2d, JC,P = 5 Hz, 2 ꢂ CH2), 62.4 (C-6), 15.8
(2d, 2 ꢂ CH3); 31P NMR (CDCl3) d: 22.9; HRMS-
ESI calcd for C38H37NaO12PS [M+Na]+: 771.1636.
Found: 771.1644. Anal. Calcd for C38H37O12PS:
C, 60.96; H, 4.98; S, 4.28. Found: C, 60.75; H, 4.83; S,
4.51.
1.3.7. O,O 0-Dibutyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-manno-
pyranosyl) thiophosphate (10). 31P NMR (CDCl3) d:
23.4. HRMS-ESI calcd for C42H45NaO12PS [M+Na]+:
827.2262. Found: 827.2301.
1.3.3. O,O 0-Diethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-manno-
1.3.8.
O-Methyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-gluco-
20
pyranosyl) thiophosphate (7). ½aꢁD ꢀ80.3 (c 0.5,
pyranosyl) phenylthiophosphonate (11). Obtained as a
mixture of diastereoisomers 11a and 11b in a ratio of
1.2:1.0. H NMR (CDCl3) d: 5.95 (t, 1H, J3,2 = J3,4
CHCl3); 1H NMR (CDCl3) d: 6.01 (m, 2H, J4,3
=
1
J4,5 = 10.1 Hz, H-2, H-4), 5.66 (m, 2H, J1,2 = 1.1,
=
JH,P = 12.5, J3,2 = 3.3 Hz, H-1, H-3), 4.73 (dd, 1H,
9.5 Hz, H-3, 11b), 5.88 (t, 1H, J3,2 = J3,4 = 9.4 Hz,
H-3, 11b), 5.62–5.75 (m, 4H, H-2, H-4, both isomers),
5.51 (dd, 1H, J1,2 = 10.2, JH,P = 11.8 Hz, H-1, 11b),
5.32 (t, 1H, J1,2 = JP,H = 10.3 Hz, H-1, 11a), 4.55 (dd,
0
J6,5 = 2.5, J6,5 = 12.3 Hz, H-6), 4.48 (dd, 1H, J6 ,5
=
4.7 Hz, H-60), 4.29 (m, 1H, H-5), 4.10–4.25 (m, 4H,
2 ꢂ CH2), 1.33 (dt, 3H, J = 7.1, JH,P = 0.8 Hz, CH3),
1.28 (dt, 3H, J = 7.1, JH,P = 0.9 Hz, CH3); 13C NMR
(CDCl3) d: 166.0 (C@O), 165.5 (C@O), 165.3 (C@O),
165.2 (C@O), 82.4 (d, JC,P = 2.6 Hz, C-1), 76.8, 72.6,
71.8 (d, JC,P = 8.5 Hz), 66.0, 64.3 (d, JC,P = 5.2 Hz,
CH2), 64.1 (d, JC,P = 5.6 Hz, CH2), 62.9 (C-6); 31P
NMR (CDCl3) d: 23.2. HRMS-ESI calcd for C38H37-
NaO12PS [M+Na]+: 771.1636. Found: 771.1614. Anal.
Calcd for C38H37O12PS: C, 60.96; H, 4.98; S, 4.28.
Found: C, 60.04; H, 4.93; S, 4.20.
0
1H, J6,5 = 2.8, J6,6 = 12.4 Hz, H-6, 11b), 4.45 (m, 2H,
0
H-6, H-6, both isomers), 4.36 (dd, 1H, J6 5 = 5.2,
0
J6,6 = 12.4 Hz, H-6, 11a), 4.25 (m, 1H, H-5, 11b), 4.17
(m, 1H, H-5, 11a), 3.82 (d, 3H, JH,P = 12.9 Hz, OCH3,
11b), 3.73 (d, 3H, JH,P = 12.8 Hz, OCH3, 11a); 13C
NMR (CDCl3) d: 83.3 (d, JC,P = 2.2 Hz, C-1, 11a),
82.9 (d, JC,P = 2.6 Hz, C-1, 11b), 76.6 (11b), 76.5 (11a),
74.0 (11b), 73.8 (11a), 71.2 (d, JC,P = 7.3 Hz, 11b), 71.1
(d, JC,P = 8.2 Hz, 11a), 69.1, 63.0 (C-6, 11a), 62.9 (C-6,
11b), 52.5 (d, JC,P = 6.9 Hz, OCH3, 11b), 52.4 (d,
JC,P = 7.3 Hz, OCH3, 11a); 31P NMR (CDCl3) d: 42.9
(11a), 41.1 (11b); HRMS-ESI calcd for C41H35NaO11PS
[M+Na]+: 789.1530. Found: 789.1551.
1.3.4. O,O 0-Diethyl-S-(2,3,4,6-tetra-O-benzoyl-a-D-manno-
20
pyranosyl) thiophosphate (20). ½aꢁD ꢀ3.1 (c 0.8,
CHCl3); 1H NMR (CDCl3) d: 6.18 (t, 1H, J4,3
=
J4,5 = 10.0 Hz, H-4), 6.03 (dd, 1H, J1,2 = 1.7,
JH,P = 12.5 Hz, H-1), 5.87 (dd, 1H, J2,3 = 3.2 Hz,
H-2), 5.82 (ddd, 1H, JH,P = 1.4 Hz, H-3), 4.67 (m,
2H), 4.53 (m, 1H), 4.25 (m, 4H, 2 ꢂ CH2), 1.38 (m,
6H, 2 ꢂ CH3); 13C NMR (CDCl3) d: 166.0 (C@O),
165.5 (C@O), 165.3 (C@O), 165.1 (C@O), 83.1 (d,
JC,P = 2.5 Hz, H-1), 72.4 (d, JC,P = 9.4 Hz), 71.4, 69.9,
66.4, 64.3 (2 ꢂ d, 2 ꢂ CH2), 62.5 (C-6), 16.0 (2 ꢂ d,
2 ꢂ CH3); 31P NMR (CDCl3) d: 22.1; HRMS-ESI calcd
for C38H37NaO12PS [M+Na]+: 771.1636. Found:
771.1621. Anal. Calcd for C38H37O12PS: C, 60.96; H,
4.98; S, 4.28. Found: C, 60.94; H, 4.82; S, 4.32.
1.3.9. O-Methyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-galacto-
pyranosyl) phenylthiophosphonate (12). Obtained as a
mixture of diastereoisomers 12a and 12b in a ratio of
1
1.1:1.0. H NMR (CDCl3) d: 6.04 (dd, 1H, J4,3 = 3.4,
J4,5 = 1.1 Hz, H-4, 12b), 6.01 (dd, 1H, J4,3 = 3.4,
J4,5 = 1.0 Hz, H-4, 12a), 5.95 (t, 1H, J2,1 = J2,3
10.0 Hz, H-2, 12b), 5.89 (t, 1H, J2,1 = J2,3 10.0 Hz,
H-2, 12a), 5.67 (dd, 1H, H-3, 12b), 5.60 (dd, 1H, H-3,
12a), 5.51 (dd, 1H, JP,H = 12.1 Hz, H-1, 12b), 5.33 (dd,
1H, JH,P = 11.1 Hz, H-1, 12a), 4.57 (dd, 1H, J6,5 = 6.7,
0
J6,6 = 11.1 Hz, H-6, 12b), 4.48 (dd, 1H, J6,5 = 6.6,

790
M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
0
J6,6 = 11.1 Hz, H-6, 12a); 4.43 (m, 1H, H-5, 12b); 4.33–
4.39 (m, 2H, J6,5 = 6.1 Hz, H-5, H-6), 4.29 (dd, 1H,
J6,5 = 5.6 Hz, H-6, 12a), 3.80 (d, 3H, JP,H = 12.0 Hz,
OCH3, 12a), 3.77 (d, 3H, JP,H = 11.3 Hz, OCH3, 12b);
13C NMR (CDCl3) d: 83.9 (d, JC,P = 2.6 Hz, C-1, 12a),
83.2 (d, JC,P = 3.0 Hz, C-1, 12b), 75.6, 72.5 (12b), 72.4
(12a), 68.7 (2 ꢂ d), 68.2, 62.3 (C-6, 12a), 62.1 (C-6,
O11PS: C, 64.61; H, 4.78; S, 4.11. Found: C, 64.68; H,
4.52; S, 4.07.
1.3.12. O-Ethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-galacto-
pyranosyl) phenylthiophosphonate (15). Obtained as a
mixture of diastereoisomers 15a and 15b in a ratio of
1
1.5:1.0. H NMR (CDCl3) d: 6.04 (dd, 1H, J4,3 = 3.4,
12b), 52.7 (d, JC,P = 5.6 Hz, OCH3), 52.1 (d, JC,P
=
J4,5 = 1.0 Hz, H-4, 15b), 6.01 (dd, 1H, J4,3 = 3.4,
J4,5 = 1.0 Hz, H-4, 15a), 5.94 (t, 1H, J2,1 = J2,3
10.1 Hz, H-2, 15b), 5.89 (t, 1H, J2,1 = J2,3 10.0 Hz,
H-2, 15a), 5.67 (dd, 1H, H-3, 15b), 5.63 (dd, 1H, H-3,
15a), 5.51 (dd, 1H, JP,H = 12.1 Hz, H-1, 15b), 5.42 (dd,
1H, JH,P = 11.3 Hz, H-1, 15a), 4.56 (dd, 1H, J6,5 = 6.6,
6.4 Hz, OCH3); 31P NMR (CDCl3) d: 42.7 (12a), 41.3
(12b); HRMS-ESI calcd for C41H35NaO11PS [M+Na]+:
789.1530. Found: 789.1555.
1.3.10. O-Methyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-manno-
pyranosyl) phenylthiophosphonate (13). Obtained as a
mixture of diastereoisomers 13a and 13b in a ratio of
0
J6,6 = 11.1 Hz, H-6, 15b), 4.47 (dd, 1H, J6,5 = 6.5,
0
J6,6 = 11.1 Hz, H-6, 15a), 4.43 (m, 1H, H-5, 15b), 4.38
1
1.2:1.0. H NMR (CDCl3) d: 6.02 (m, 3H, H-2, H-2,
(m, 1H, H-5, 15a), 4.00–4.30 (m, other protons), 1.28
(t, 3H, J = 7.0 Hz, CH3, 15b), 1.19 (t, 3H, J = 7.0 Hz,
CH3, 15a); 13C NMR (CDCl3) d: 84.0 (d, JC,P <1 Hz,
C-1, 15a), 83.4 (d, JC,P <1 Hz, C-1, 15b), 75.6 (15b),
75.5 (15a), 72.5 (15b), 72.4 (15a), 68.8 (2 ꢂ d), 68.2,
62.6 (2 ꢂ d, 2 ꢂ CH2), 62.2 (C-6, 15a), 62.1 (C-6, 15b),
16.1 (CH3, 15b), 16.0 (CH3, 15a); 31P NMR (CDCl3)
d: 40.4 (15a), 39.0 (15b); HRMS-ESI calcd for
C42H37O11NaPS [M+Na]+: 803.1686. Found: 803.1691.
Anal. Calcd for C42H37O11PS: C, 64.61; H, 4.78; S,
4.11. Found: C, 64.52; H, 4.69; S, 4.10.
H-4), 5.97 (t, 1H, J4,3 = J4,5 = 10.0 Hz, H-4), 5.77 (dd,
1H, J1,2 = 1.1, JH,P = 11.2 Hz, H-1, 13b), 5.69 (dd, 1H,
J3,2 = 3.3, J3,4 = 10.3 Hz, H-3, 13b), 5.62 (m, 2H,
J1,2 = 1.1, J3,2 = 3.3, JH,P = 11.2 Hz, H-1, H-3, 13a),
4.70 (dd, 1H, J6,5 = 2.4, J6,6 = 12.3 Hz, H-6, 13b), 4.54
(dd, 1H, J6,5 = 2.6, J6,6 = 12.3 Hz, H-6, 13a), 4.47 (dd,
0
0
0
0
1H, J6 ,5 = 4.8 Hz, H-6, 13b), 4.40 (dd, 1H, J6 ,5
=
4.8 Hz, H-6, 13a), 4.29 (m, 1H, H-5, 13b), 4.19 (m,
1H, H-5, 13a), 3.91 (d, 3H, JH,P = 12.6 Hz, OCH3,
13a), 3.90 (d, 3H JH,P = 12.8 Hz, OCH3, 13b); 13C
NMR (CDCl3) d: 82.1 (bs, JC,P <1 Hz, C-1, 13a), 81.2
(d, JC,P = 2.1 Hz, C-1, 13b), 76.8 (13a), 76.7 (13b), 72.7
(13b), 72.6 (13a), 72.0 (d, JC,P = 6.8 Hz, 13b), 71.8 (d,
JC,P = 6.8 Hz, 13a), 66.1, 62.9 (C-6, 13a), 62.8 (C-6,
1.3.13. O-Ethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-manno-
pyranosyl) phenylthiophosphonate (16). Obtained as a
mixture of diastereoisomers 16a and 16b in a ratio of
1
13b), 52.8 (d, JC,P = 2.6 Hz, OCH3), 52.7 (d, JC,P
=
1.3:1.0. H NMR (CDCl3) d: 5.94–6.05 (m), 5.76 (dd,
2.6 Hz, OCH3); 31P NMR (CDCl3) d: 43.1 (13a), 41.1
(13b); HRMS-ESI calcd for C41H35NaO11PS
[M+Na]+: 789.1530. Found: 789.1559. Anal. Calcd for
C41H35O11PS: C, 64.22; H, 4.60; S, 4.18. Found: C,
64.51; H, 4.83; S, 3.79.
J = 1.0 and 11.1 Hz), 5.62–5.70 (m), 4.69 (dd, J = 2.5
and 12.4 Hz), 4.15–4.53 (m), 1.39 (t, J = 7.0 Hz, CH3,
16a), 1.32 (t, J = 7.0 Hz, CH3, 16b); 13C NMR (CDCl3)
d: 82.1 (C-1, 16a), 81.3 (C-1, 16b), 76.7, 72.7, 72.6, 71.9,
71.8, 66.1, 62.9 (CH2), 16.3; 31P NMR (CDCl3) d: 41.1
(16a), 38.8 (16b); HRMS-ESI calcd for C42H37O11NaPS
[M+Na]+: 803.1686. Found: 803.1725. Anal. Calcd for
C42H37O11PS: C, 64.61; H, 4.78; S, 4.11. Found: C,
64.55; H, 4.69; S, 4.19.
1.3.11. O-Ethyl-S-(2,3,4,6-tetra-O-benzoyl-b-D-glucopyr-
anosyl) phenylthiophosphonate (14). Obtained as a mix-
ture of diastereoisomers 14a and 14b in a ratio of 1.3:1.0.
1H NMR (CDCl3) d: 5.93 (t, 1H, J3,2 = J3,4 = 9.4 Hz,
H-3, 14a), 5.89 (t, 1H, J3,2 = J3,4 = 9.4 Hz, H-3, 14b),
5.62–5.74 (m, 4H, H-2, H-4), 5.49 (dd, 1H, J1,2 = 10.1,
1.3.14. O-Ethyl-S-(2,3,4,6-tetra-O-benzoyl-a-D-manno-
pyranosyl) phenylthiophosphonate (21). Obtained as a
mixture of diastereoisomers 21a and 21b in a ratio of
JH,P = 11.9 Hz, H-1, 14a), 5.40 (t, 1H, J1,2 = JP,H
10.4 Hz, H-1, 14b), 4.53 (dd, 1H, J6,5 =2.8, J6,6
=
=
1
0
1.3:1.0. H NMR (CDCl3) d: 6.18 (m, 3H, H-1, H-4),
12.3 Hz, H-6, 14a), 4.42 (m, 2H, H-6, H-6, 14ab), 4.34
6.00 (dd, 1H, J1,2 = 0.8, JH1,P = 10.4 Hz, H-1, 21b),
5.90 (dd, 1H, J2,3 = 3.1 Hz, H-2, 21a), 5.76–5.84 (m,
3H), 4.59 (m, 1H, H-5, 21b), 4.32–4.46 (m, 6H), 4.28
0
0
0
(dd, 1H, J6 5 = 5.0, J6,6 = 12.3 Hz, H-6, 14b), 4.00–
4.30 (m, other protons), 1.28 (t, 3H, J = 7.1 Hz, CH3,
14a), 1.18 (t, 3H, J = 7.1 Hz, CH3, 14b); 13C NMR
(CDCl3) d: 83.5 (d, JC,P <1 Hz, C-1, 14b), 83.0 (d,
JC,P = 2.6 Hz, C-1, 14a), 76.6 (14b), 76.5 (14a), 74.0
(14a), 73.8 (14b), 71.2 (2d), 69.1, 63.0 (C-6, 14b), 62.9
(C-6, 14a), 62.6 (2d, 2 ꢂ CH2), 16.1 (CH3, 14b), 16.0
(CH3, 14a); 31P NMR (CDCl3) d: 40.6 (14b), 38.9
(14a); HRMS-ESI calcd for C42H37O11NaPS [M+Na]+:
803.1686. Found: 803.1725. Anal. Calcd for C42H37-
(m, 1H, H-5, 21a), 4.11 (dd, 1H, J6,5 = 1.8, J6,6
=
0
12.5 Hz, H-6, 21a), 3.95 (dd, 1H, J6 ,5 = 2.6 Hz, H-6,
21a), 1.45 (2t, 6H, 2 ꢂ CH3); 13C NMR (CDCl3) d:
83.2 (C-1, 21a), 82.2 (C-1, 21b), 72.5 (d, JC,P = 7.7 Hz,
21b), 71.9 (d, JC,P = 7.7 Hz, 21a), 71.0 (21a), 70.6
(21b), 70.2 (21a), 70.1 (21b), 66.3 (21b), 66.2 (21a),
63.3 (d, JC,P = 6.8, CH2, 21a), 62.8 (d, JC,P = 6.9 Hz,
CH2, 21a), 62.2 (C-6, 21b), 61.6 (C-6, 21b), 16.3 (21a),

M. Piekutowska, Z. Pakulski / Carbohydrate Research 343 (2008) 785–792
791
16.2 (21b); 31P NMR (CDCl3) d: 39.2 (21a), 39.1 (21b);
HR-MS (ESI) calcd for C42H37O11NaPS [M+Na]+:
803.1686. Found: 803.1724. Anal. Calcd for C42H37-
O11PS: C, 64.61; H, 4.78; S, 4.11. Found: C, 64.65; H,
4.60; S, 4.24.
1.3.19. 2,3,4,6-Tetra-O-benzoyl-1-thio-a-D-mannopyran-
20 20
ose (23). ½aꢁD ꢀ30.5 (c 0.5, CHCl3); Lit:16 ½aꢁD ꢀ30.5
(c 1.0, CHCl3); 1H and 13C NMR spectral data matched
that reported.16
Acknowledgement
1.3.15. S-(2,3,4,6-Tetra-O-benzoyl-b-D-glucopyranosyl)
20
diphenylthiophosphinate (17). ½aꢁD +43.0 (c 0.4,
1
This work was supported by Grant 3 TO9A 110 29 from
the Ministry of Science and Higher Education, Poland.
CHCl3); H NMR (CDCl3) d: 5.88 (t, 1H, J3,2 = 9.5,
J3,4 = 9.5 Hz, H-3), 5.70 (m, 2H, J2,1 = 9.7 Hz,
J4,5 = 9.8 Hz, H-2, H-4), 5.53 (t, 1H, JPH = 9.5 Hz,
H-1), 4.16 (m, 2H, H-6, H-60), 4.01 (m, 1H, H-5); 13C
NMR (CDCl3) d: 165.9 (C@O), 165.5 (C@O), 165.3
(C@O), 165.0 (C@O), 81.2 (C-1), 76.3, 74.1, 71.4 (d,
JC,P = 6.1 Hz), 68.9, 62.6 (C-6); 31P NMR (CDCl3) d:
42.4. HRMS-ESI calcd for C46H37NaO10PS [M+Na]+:
835.1737. Found: 835.1704. Anal. Calcd for C46H37-
O10PS: C, 67.97; H, 4.59; S, 3.94. Found: C, 67.68; H,
4.41; S, 4.07.
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J4,5 <1 Hz, H-2, H-4), 5.63 (dd, 1H, J3,2 = 9.9 Hz,
H-3), 5.52 (t, 1H, J1,2 = JH,P = 10.3 Hz, H-1), 4.22 (m,
0
2H, H-5,6), 4.12 (dd, 1H, J6,5 = 8.7, J6 6 = 13.1 Hz,
H-60); 13C NMR (CDCl3) d: 165.8 (C@O), 165.5 (C@O),
165.4 (C@O), 165.3 (C@O), 81.6 (C-1), 75.2, 72.5, 68.9
(d, JC,P = 6.8 Hz), 68.2, 61.6 (C-6); 31P NMR (CDCl3)
d: 42.4; HRMS-ESI calcd for C46H37NaO10PS
[M+Na]+: 835.1737. Found: 835.1728. Anal. Calcd for
C46H37O10PS: C, 67.97; H, 4.59; S, 3.94. Found: C,
67.88; H, 4.63; S, 3.77.
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20
´
diphenylthiophosphinate (19). ½aꢁD ꢀ74.3 (c 0.3,
687–691; (d) Borowiecka, J.; Stanczak, A. Il Farmaco
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J4,5 = 10.1 Hz, H-2, H-4), 5.73 (dd, 1H, J1,2 = 1.1,
JH,P = 10.5 Hz, H-1), 5.64 (dd, 1H, J3,2 = 3.3 Hz, H-
0
3), 4.29 (dd, 1H, J6,5 = 2.7, J6,6 = 12.2 Hz, H-6), 4.22
(dd, 1H, J6 ,5 = 3.7 Hz, H-60), 3.99 (m, 1H, H-5); 13C
0
NMR (CDCl3) d: 165.9 (C@O), 165.3 (C@O), 165.2
(C@O), 165.1 (C@O), 79.6 (d, JC,P = 1.7 Hz, H-1),
76.5, 72.6, 72.2 (d, JC,P 6.0 Hz), 65.9, 62.5 (C-6); 31P
NMR (CDCl3) d: 43.1; HRMS-ESI calcd for C46H37-
NaO10PS [M+Na]+: 835.1737. Found: 835.1726. Anal.
Calcd for C46H37O10PS: C, 67.97; H, 4.59; S, 3.94.
Found: C, 67.71; H, 4.62; S, 4.20.
1.3.18. S-(2,3,4,6-Tetra-O-benzoyl-a-D-mannopyranosyl)
diphenylthiophosphinate (22). 13C NMR (CDCl3) d:
165.9 (C@O), 165.5 (C@O), 165.1 (C@O), 164.8
(C@O), 81.4 (C-1), 72.0 (d, J = 6.8 Hz), 70.8, 70.4,
66.3, 61.8 (C-6); 31P NMR (CDCl3) d: 40.6; HRMS-
ESI calcd for C46H37NaO10PS [M+Na]+: 835.1737.
Found: 835.1721.
_
´
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