Synthesis of phosphorylated derivatives of sucrose: 6,6′-di- phosphonate, 6- and 6′-phosphonates, and 6,6′-di-phosphine

Article abstract of DOI:10.1080/07328303.2010.524958

Reaction of 6,6′dideoxy-6,6′di-iodo-1′,2,3,3′,4, 4′-hexa-O-benzylsucrose with triethyl phosphite afforded the corresponding 6,6′-diphosphonate. Selective phosphonylation either at the C-6 or 6-6′ position was also possible providing the corresponding sucrose mono-phosphonates. Reaction of 6,6′-dichloro-hexa-O-benzylsucrose with diphenylphoshine anion afforded the 6,6′-diphosphinosucrose. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/07328303.2010.524958

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Synthesis of Phosphorylated Derivatives
of Sucrose: 6,6′-di-Phosphonate, 6- and
6′-Phosphonates, and 6,6′-di-Phosphine
Anna Gaweł a & Sławomir Jarosz a
a Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224, Warszawa
Version of record first published: 13 Dec 2010.
To cite this article: Anna Gaweł & Sławomir Jarosz (2010): Synthesis of Phosphorylated Derivatives
of Sucrose: 6,6′-di-Phosphonate, 6- and 6′-Phosphonates, and 6,6′-di-Phosphine, Journal of
Carbohydrate Chemistry, 29:7, 332-347
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Journal of Carbohydrate Chemistry, 29:332–347, 2010
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Copyright Taylor & Francis Group, LLC
ISSN: 0732-8303 print / 1532-2327 online
DOI: 10.1080/07328303.2010.524958
Synthesis of Phosphorylated
Derivatives of Sucrose:
6,6ꢁ-di-Phosphonate, 6- and
6ꢁ-Phosphonates, and
6,6ꢁ-di-Phosphine
Anna Gaweł and Sławomir Jarosz
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,
01-224 Warszawa
Reaction of 6,6ꢁdideoxy-6,6ꢁdi-iodo-1ꢁ,2,3,3ꢁ,4,4ꢁ-hexa-O-benzylsucrose with triethyl
phosphite afforded the corresponding 6,6ꢁ-diphosphonate. Selective phosphonylation
either at the C-6 or 6-6ꢁ position was also possible providing the correspond-
ing sucrose mono-phosphonates. Reaction of 6,6ꢁ-dichloro-hexa-O-benzylsucrose with
diphenylphoshine anion afforded the 6,6ꢁ-diphosphinosucrose.
Keywords Sucrose; Sucrose phosphonates; Sucrose phosphines
Sucrose (α-D-fructofuranosyl β-D-glucopyranoside), the most available low-
weight carbohydrate, is absorbed mostly by the food market, but efforts have
also been put forward to use this compound as a chemically reactive organic
raw material.[1–3] The main problems encountered during work with sucrose
are very high sensitivity of the glycosidic bond toward acids,[1,4] poor solubility
in organic solvents, and similar reactivity of the eight hydroxyl groups present
in the molecule. Only differentiation between the primary and secondary
OH groups is relatively straightforward: 1ꢁ,6,6ꢁ-tri-O-trityl[5] and 1ꢁ,6,6ꢁ-tri-O-
silylated[6,7] sucroses are obtained in good yields by reaction of sucrose with
an excess of trityl or silyl chlorides. It is also worth pointing out the very high
affinity of the 6ꢁ-OH group toward the silylating agents, which allows prepar-
ing 6ꢁ-O-monoprotected sucrose in good yield.[7]
Received July 29, 2010; accepted September 15, 2010.
Address correspondence to Sławomir Jarosz, Institute of Organic Chemistry, Polish
Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa. E-mail: sljar@icho.edu.pl
332

Synthesis of Phosphorylated Derivatives of Sucrose
333
As a part of an ongoing program in the application of sucrose as a
fine chemical, we have elaborated a convenient route to 1ꢁ,2,3,4,3ꢁ,4ꢁ-hexa-O-
benzylsucrose (1),[2] in which all secondary hydroxyl groups and the less re-
active primary one (at the C1ꢁ-position) were protected with the benzyl blocks
easily removable under neutral conditions. The diol 1 is a convenient start-
ing material for the preparation of crown and aza-crown ether analogues,[2,8]
showing interesting complexing abilities toward the ammonium cation[8] and
significant enantioselectivity in complexation of α-phenylethylamine (e.g., 2;
X = Y = Z = NBn).[9]
Diol 1 was also used for the preparation of sulphated sucroses. Either the
bi-sulphide (3)[10] or the monosulphide (4) was obtained; the latter was easily
dimerized to the disulphide (6),[11] which can be used for the preparation of the
sulphated macrocycles with sucrose scaffold (Fig. 1).
The diol 1, which is used for the synthesis of compounds of type 2–6, is
prepared from di-O-tritylsucrose 7, obtained by selective tritylation of free su-
crose. However, isolation of the intermediate 7 requires extensive chromato-
graphic purification.[2] We have succeeded now in an efficient isolation of di-
O-tritylsucrose 7 without any chromatographic method. Also, the hydrolysis of
the trityl ethers in 8 was optimized (Sch. 1; for detailed procedure see Experi-
mental).
Exploring the chemistry of sucrose, we turned our attention to the phos-
phorous analogues of this disaccharide. Sucrose phosphines might be, eventu-
ally, applied as ligands in asymmetric synthesis.[12] On the other hand, the
sucrose phosphonates are important targets, since some of them [with the
C(6) O P C bond] possess very interesting biological activity.[13]
The Arbuzov reaction was designed to prepare the phosphonate analogues
of sucrose. Hexa-O-benzyl-6,6ꢁ-di-chlorosucrose (9)[10] seemed to be the most
Figure 1: Synthesis of fine chemicals from sucrose.

A. Gaweł & S. Jarosz
334
Scheme 1: i. TrCl, DMAP (cat.), py. r.t., 44%; ii. BnBr, NaH, DMF, r.t., 93%; iii. l2/MeOH, CH2Cl2,
reflux, 42%.
convenient starting material for the model preparation of the di-phosphonate
10, but reaction of this compound either with triethyl or diethyl trimethylsilyl
phosphite did not afford any product. We decided, therefore, to apply the di-
iodosucrose 11, easily prepared from the corresponding diol 1, under the stan-
dard conditions (see Experimental section); this compound was also prepared
from dichloro-derivative 9 by reaction with excess potassium iodide. Reac-
tion of the di-iodo derivative 11 with excess (EtO)3P afforded the desired di-
phosphonate 10 in 24% yield (Sch. 2).
Scheme 2: i. (EtO)3P, reflux, 24 h; ii. (EtO)2P(OTMS), 60◦C, 48 h; iii. Kl (excess), DMF, 120◦C, 72 h,
66%; iv. 1. MsCl, Et3N, DMAP, CH2Cl2, r.t. 85%; 2. Kl (excess, DMF, 90◦C, 36 h, 98%; v. Kl (1 equiv.),
DMF, 120◦C, 12 h ratio 12 : 13 = 25 : 1 (23% 12).
It is known that the 6- and 6ꢁ-positions in sucrose have different reactivity
toward some reagents (such as silyl chlorides). We have observed similar regio-
selectivity in reaction of di-chloride with iodide anion, which might open a
convenient route to sucrose mono-phosphorous derivatives.
Reaction of 9 with one equiv. of KI afforded a mixture of mono-iodides 12
and 13 with the preponderance of the 6-iodo-6ꢁ-chloro-derivative 12. These two
regioisomers could not, however, be separated even by HPLC, so the assign-
ment of their structure was performed on the mixture.
In the mass spectrum, the signal m/z 1033 was found, which could be as-
signed to chloro-iodo-hexa-O-benzyl-sucrose [M (C54H56ClIO9)+Na+ = 1010 +
23]. Two signals of the H-1 protons from 12 and 13 (at δ = 5.68 and 5.64 ppm)

Synthesis of Phosphorylated Derivatives of Sucrose
335
allowed us to establish the ratio of both regioiosomers at 2.5:1. The position
of iodine at the “glucose end” (C6) was determined by NMR correlations. The
anomeric proton in the main isomer (δ = 5.68 ppm) could be (via COSY cross-
peaks) connected to the H5 (m, δ = 3.40), which correlated to both H6 of the
glucose part at δ: 3.29 (dd, 1H, J6a,4 = 3.9, J6b,6a = 10.9 Hz) and 3.20 (dd, 1H,
J6b,4 = 2.8 Hz) ppm. The HETCOR spectrum showed the cross-peaks of these
two protons to the carbon resonance at δ = 9.31 ppm, which was assigned to
the CH2 I group. Analogously, the H-1 signal of the minor regioisomer 13
(at δ = 5.64 ppm) could be correlated with the 13C resonance at δ = 6.15 ppm,
which had much lower intensity than the signal at δ = 9.32 ppm. Thus, the
major isomer had structure 12 and, consequently, structure 13 was assigned
to the minor one.
Because we were not able to isolate these two regioisomers in pure form,
another route to sucrose monophosphonates was elaborated.
The synthesis was initiated from the diol 1. Taking advantage of the known
affinity of the 6ꢁ-OH toward the silylating agents (either in free[7] or partially
protected sucrose[2,14]), the monoalcohol 15 was prepared in good yield.[14] The
regioisomeric (to 15) alcohol 16 was prepared by selective desilylation∗ of the
double protected derivative 14 as shown in Scheme 3.
Scheme 3: i. TPSCl (2.5 equiv.), DIPEA, DMAP (cat), CH2Cl2, r.t., 80%; ii. TPSCl (2 equiv.), DIPEA,
DMAP (cat.), CH2Cl2, r.t., 62%; iii. Bu4NF 3H2O, THF, r.t. 58%.
Synthesis of both monophosphates was performed according to the same
methodology. Thus, activation of the hydroxyl group either in 15 or 16 pro-
vided the corresponding mesylates 17 and 18, which were then converted
into iodides 19 and 20 by reaction with potassium iodide. Further reaction
of these intermediates with triethyl phosphite performed under reflux af-
forded finally the desired (mono-silylated) phosphonates 21 (87% yield) and 22
(45% yield).
Removal of the silyl protection from the 6-phosphonate 21 was possible and
afforded the free alcohol 21a in good yield. Much more difficult was deprotec-
tion of the regioisomeric phosphonate 22; under the standard conditions only
traces of alcohol 22a (detectable by MS) were obtained (Sch. 4).
Next we turned our attention to the synthesis of sucrose phoshines, which
were initiated from the perbenzylated dichlorosucrose 9, readily available in

A. Gaweł & S. Jarosz
336
Scheme 4: i. MsCl, py, r.t. (87% of 17, 93% of 18); ii. Kl, DMF, 120◦C, (89% of 19, 44% of 20);
iii. (EtO)3P, reflux, (88% of 21, 45% of 22); iv. Bu4NF · 3H2O, THF, 60◦C, 74%; v. Bu4NF, KOH, MeOH,
r.t., traces.
our laboratory.[10] Reaction of 9 with the diphenylphosphine anion (generated
from either Ph2PH/Na[15] or Ph3P/Na[16]) afforded sucrose diphosphine 23,
which usually was contaminated with the oxidation product 24. Presence of
both species was detected easily by the 31P NMR spectra in which the charac-
teristic signals for phosphine δ = −22.1 and −24.8 ppm) in 23 and phosphine
oxide δ = +29.3 and +28.4 ppm) in 24 were seen (Sch. 5).
Scheme 5: i. Ph3P/Na, THF, 30 min. r.t., then 9, overnight (29% of 23); ii. Ph2PH/Na, THF, 30 min.
then 9 overnight r.t. (5% of 23, 27% of 24); iii. Mel, than LAH, THF, r.t., 24 h, 49%; iv. H2O2,
acetone, r.t., 24 h, quant.

Synthesis of Phosphorylated Derivatives of Sucrose
337
The undesired di-phosphine oxide 24 was easily reduced to di-phosphine
23 with lithium aluminum hydride. Alternatively, the phosphine 23 was quan-
titatively oxidized to di-oxide 24 with hydrogen peroxide (see Experimental
section).
CONCLUSION
Proper functionalization of the C-6 and C-6ꢁ “ends” in hexa-O-benzyl sucrose
provided the phosphorous analogues of sucrose, either phosphonates or phos-
phines. Regioselective introduction of the phosphorous atom either at the C-6
or C-6ꢁ positions was also performed in good yield. The methodology presented
in this paper allows for the introduction of the phosphorous atom at both (C-6
and C-6ꢁ) terminal positions and also preparation of sucrose mono-phosphates.
EXPERIMENTAL
The NMR spectra were measured in CDCl3 solutions (internal Me4Si) with the
following spectrometers: Bruker DRX 500, Varian-NMR-vnmrs600, and Varian
Merkury 400. The assignment of the 1H and 13C NMR signals was made using
results of 2D methods including COSY, HSQC, and DEPT correlations. The
1H and 13C aromatic resonances occurring at the typical δ values were omit-
1
ted for simplicity. In the H NMR spectra only diagnostic signals are shown.
Mass spectra were recorded with an ESI/MS Mariner (PerSeptive Biosystem)
mass spectrometer. Optical rotations were measured with a Jasco P-1020 or
P-2000 polarimeter (λ = 589 nm) for solutions in CHCl3 (c = 1) at rt (un-
less otherwise stated). Column chromatography was performed on silica gel
(Merck, 70–230 mesh). Methylene chloride was distilled from CaH2 and THF
from potassium prior to use. Organic solutions were dried over anhydrous mag-
nesium or sodium sulphate.
Improved preparation of 1,2,2ꢀ,3,3ꢀ,4,4ꢀ-hexa-O-
benzylsucrose (1)
Synthesis of 6,6ꢁ-di-O-tritylsucrose (7)
A suspension of sucrose (10 g, 29 mmol) in pyridine (170 mL) was boiled
under reflux until all material dissolved (10 min) and the clear solution was
cooled to rt. Trityl chloride (19 g, 68 mmol) and a catalytic amount of DMAP
(0.1 g) were added and the reaction mixture was stirred at rt for 3 days. After
this time TLC (ethanol/ethyl acetate/water, 45:5:3) indicated formation of the
desired (previously synthesized ref. [10,17]) di-O-tritylsucrose 3 and side prod-
ucts (tri-O-trityl and several mono-O-trityl derivatives). An excess of pyridine
was removed under reduced pressure, and the residue was partitioned between

A. Gaweł & S. Jarosz
338
water (200 mL) and ethyl acetate (200 mL). The organic solution was sepa-
rated and the aqueous phase extracted with ethyl acetate (2 × 200 mL). Com-
bined organic solutions were dried and concentrated, and a syrupy residue was
partitioned between toluene (200 mL) and methanol/water (200 mL, 1:1 v/v).
Two phases were separated; toluene one was collected and aqueous/methanolic
was discarded. Toluene phase (containing 7, tri-O-trityl-sucroses, trityl chlo-
ride, and trityl alcohol) was washed with aqueous methanol (3 × 200 mL, 1:1
v/v), dried, and concentrated. The residue—a yellowish foam—was dissolved
in toluene (90 mL), to which methanol (130 mL) and water (40 mL) were
added. Two phases were formed. The aqueous methanolic phase (containing
mostly the desired 7) was separated and the toluene one extracted with aque-
ous methanol (2 × 170 mL, 3:1 v/v). Combined methanolic fractions were con-
centrated, the residue was dissolved in a small amount of methanol, and 7
crystallized. The white product crystals formed were filtered and dried to af-
ford the title derivative 7 in 44% yield. [α]D = 39.5.
The six hydroxyl groups in 7 were protected as benzyl ethers (to provide 8)
as described previously.[18]
Removal of trityl blocks from 8
Usually this deprotection is performed with acetic acid.[10,18] However,
the procedure sometimes may cause problems resulting from hydrolysis of
the glycosidic bond. The new procedure described below allowed us to obtain
the desired diol 1 with full reproducibility. Thus, a solution of 6,6ꢁ-ditrytyl-
1ꢁ,2,3,3ꢁ,4,4ꢁ-hexa-benzylsucrose (8, 4.11 g, 3 mmol) was dissolved in methy-
lene chloride (5 mL), to which a 5% solution of iodine in methanol (50 mL)
was added and the mixture was stirred and boiled under reflux for 3.5 h. After
cooling to rt, aq. Na2S2O3 was added, followed by ethyl acetate (300 mL). The
organic phase was separated, washed with aq. 10% NaOH (until neutrality),
dried, and concentrated, and the product was isolated by column chromatog-
raphy (ethyl acetate/hexane, 1.5:1) to afford the desired diol 1 as colorless oil
(1.09 g, 1.2 mmol, 42%), identical in all respects with the product prepared by
the independent route.[13,17]
[α]D = 41.2 (lit. [α]D = 40.8).[17]
1,2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-benzyl-6,6ꢀ-dideoxy-6,6ꢀ-di-iodosucrose
(11)
Method a: To
a
stirred solution of 6,6ꢁ-dideoxy-6,6ꢁ-di-chloro-
1,2,2ꢁ,3,3ꢁ,4,4ꢁ-hexa-O-benzylsucrose[10] (9) (2.11 g, 2.3 mmol) in dry DMF
(20 mL), potassium iodide (3 g) was added, and the mixture was stirred at
120◦C for 72 h and cooled to rt. Water (30 mL) was added and the product was
extracted with diethyl ether (3 × 50 mL). Combined organic solutions were

Synthesis of Phosphorylated Derivatives of Sucrose
339
dried and concentrated, and the product 11 was isolated by column chromatog-
raphy (hexane/ethyl acetate, 8:1) as a colorless oil (1.66 g, 1.5 mmol, 66%).
[α]D = 25.3; m/z: 1125.1913 [calcd. for C54H56O9NaI (M+Na): 1125.1906];
1H NMR (500 MHz) δ: 5.64 (d, 1H, J = 3.6 Hz, H-1); 13C NMR δ: 138.6, 138.4,
138.1, 138.0, 137.8 double intensity (6 × Cquat. O CH2 Ph), 105.3 (C-2ꢁ), 90.3,
85.2, 84.6, 81.6, 81.2, 80.6, 80.0, 69.0 (C-1, C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2, C-3, C-4, C-5),
75.5, 75.2, 73.5, 73.1, 72.5 double intensity, 70.8 (6 × O CH2 Ph, C-1ꢁ), 9.5
and 6.3 (C-6ꢁ, C-6).
Anal. calc. for C54H56O9I2: C, 58.81; H, 5.12; found: C, 58.67; H, 5.27%.
Method b: To a stirred solution of the diol 1 (0.2 g, 0.23 mmol) in
dichloromethane (8 mL), triethylamine (0.1 mL, 1.4 mmol) and a catalytic
amount of DMAP (20 mg) were added. Mesyl chloride (0.1 mL, 1.2 mmol) was
added dropwise, the mixture was kept 24 h at rt and then partitioned between
water (20 mL) and ethyl acetate (30 mL). The organic phase was separated and
the aqueous one extracted with ethyl acetate (2 × 30 mL). Combined organic
solutions were dried and concentrated, and the product was purified by column
chromatography (hexane/ethyl acetate, 5:1 then 2:1) to afford the correspond-
ing di-mesylate[13] as a colorless oil (0.2 g, 0.2 mmol, 85%).
To a solution of this mesylate (0.11 g, 0.1 mmol) in dry DMF (5 mL), KI
(0.17 g, 1 mmol) was added, and the mixture was stirred at 90◦C for 36 h and
after cooling to rt partitioned between water (15 mL) and diethyl ether (15 mL).
The organic phase was separated and the aqueous one extracted with diethyl
ether (2 × 15 mL). Combined organic solutions were dried and concentrated,
and the product 11 was purified by column chromatography (hexane/ethyl ac-
etate, 8:1) as a colorless oil (0.11 g, 0.1 mmol, 96%).
6,6ꢀ-bis-(Diethoxy-phosphoryl)-6,6ꢀ-dideoxy-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-
benzylsucrose (10)
Compound 11 (1.5 g, 1.4 mmol) was dissolved in P(OEt)3 (7 mL), stirred,
and boiled under reflux in the oxygen-free atmosphere for 72 h. The excess of
P(OEt)3 was removed under vacuum (below 70◦C) and the product was puri-
fied by column chromatography (hexane/ethyl acetate, 2:1) to afford 10 as a
colorless oil (0.37 g, 0.33 mmol, 24%).
[α]D = 21.7; m/z 1145.4537 [calc. for C62H76O15P2Na (M+Na): 1145.455;
1H NMR (500 MHz) δ: 5.65 (d, 1H, J = 3.5 Hz; H-1); 31P NMR δ: 29.81, 29.10;
13C NMR δ: 138.7, 138.6, 138.3, 138.23, 138.21, 138.1 (6 × Cquat. O CH2 Ph),
105.3 (C-2ꢁ), 90.3, 85.9 (d, JCP = 12.2 Hz), 84.0 (d, JCP = 1.9 Hz), 81.6, 81.0
(d, JCP = 9.4 Hz), 80.0, 76.1 (d, JCP = 3.4 Hz), 67.0 (d, JCP = 7.0 Hz) (C-1,
C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2, C-3, C-4, C-5), 75.3, 74.7, 73.3, 73.0, 72.7, 72.3, 70.9 (6 ×
O CH2 Ph, C-1ꢁ), 61.7 (d, JCP = 6.2 Hz), 61.5 (d, JCP = 6.2 Hz), 61.4 (d, JCP
=
6.2 Hz), 61.2 (d, JCP = 6.0 Hz), 31.9 (d, JCP = 139 Hz), 27.8 (d, JCP = 142 Hz)
(4 × P OCH2 CH3, C-6, C-6ꢁ), 32.2, 16.4 (m, 4 × P OCH2 CH3).

A. Gaweł & S. Jarosz
340
Anal. xalc. for C62H76O15P2 · 0,5 H2O: C, 65.77; H, 6.85; found: C, 65.77; H,
6.57%.
6,6ꢀ-Dideoxy-6ꢀ-chloro-6-iodo- and 6,6ꢀ-dideoxy-6-chloro-
6ꢀ-iodosucrose and 1,2,2ꢀ,3,3ꢀ,4,4ꢀ-hexa-O-benzyl- sucrose
(12 and 13)
Di-chloro derivative 9 (0.6 g, 0.65 mmol) was dissolved in DMF (7.5 mL),
to which KI (0.11 g, 0.65 mmol) was added and the mixture stirred at 120◦C
for 12 h. After cooling to rt, water (15 mL) was added and product was ex-
tracted with diethyl ether (3 × 15 mL). Combined organic solutions were dried
and concentrated, and the product was isolated by HPLC (C18-column, hex-
ane/ethyl acetate, 10:1) to afford an unseparable mixture of regioisomers 12
and 13 as a colorless oil (210 mg, 0.21 mmol, 32%) in the 2.5:1 ratio.
m/z : 1033 [M(C54H56O9ClI + Na+ = 1010 + 23].
NMR data for mixture of isomers 12 and 13: 1H NMR (500 MHz) δ: 5.68 (d,
1H, J1,2 = 3.6 Hz, H-1; main isomer 12), 5.65 (d, 1H, J1,2 = 3.5 Hz, H-1; minor
isomer 13); 13C NMR δ: 105.3 and 105.2 (C-2ꢁ of 12 and C-2ꢁ of 13), 90.3 (C-1 of
12 and C-1 of 13), 45.0 (C-6ꢁ of 12 and C-6 of 13), 9.32 (much higher intensity
C-6 of 12), and 6.15 (lower intensity C-6ꢁ of 13).
1
Other selected H NMR signals of the main isomer 12: 4.0 (m, H-3), 3.52
(m, H-2), 3.40 (m, H-4, H-5), 3.29 and 3.20 (both H-6).
1,2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-benzyl-6,6ꢀ-di-O-(tert-butyldiphenylsilyl)
sucrose (14).
Compound 1 (5 g, 5.7 mmol) was dissolved in dry methylene chloride
(18 mL) containing DMAP (cat.) and DIPEA (2 mL, 11.7 mmol). tert-Butyl-
diphenylsilyl chloride (3 mL, 11.6 mmol) was added dropwise and the mixture
was stirred for 12 h at rt. Then it was partitioned between water (15 mL) and
ethyl acetate (20 mL), the organic phase was separated, and the aqueous one
was extracted with ethyl acetate (2 × 20 mL). Combined organic solutions were
dried and concentrated, and the product was purified by column chromatog-
raphy (hexane/ethyl acetate, 5:1 to 3:1) to afford 11 as a colorless oil (6.2 g,
4.6 mmol, 80%). Significant amounts (1.14 g, 1.0 mmol, 18%) of 1,2,2ꢁ,3,3ꢁ,4,4ꢁ-
hexa-O-benzyl-6ꢁ-O-(tert-butyldiphenylsilyl)sucrose[14] (15) were also formed.
1
Data for 14: [α]D = 26.0; m/z: 1383 [M(C86H94O11Si2) + Na+]; H NMR
(500 MHz) δ: 5.90 (d, 1H, J1,2 = 3.5 Hz, H-1); 13C NMR δ: 138.99, 138.95, 138.7,
138.3, 138.04 and 137.96 (6 × Cquat. O CH2 Ph), 133.7, 133.4, 133.4, 133.1
(4 × Cquat. Si-Ph), 104.5 (C-2ꢁ), 89.6 (C-1), 84.3, 82.2, 82.1, 80.7, 80.5, 77.2,
71.6 (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4, C-2, C-5), 75.7, 74.7, 73.5, 73.2, 72.6, 72.0, 71.8

Synthesis of Phosphorylated Derivatives of Sucrose
341
(6 × O CH2 Ph, C-1ꢁ), 64.6, 62.3 (C-6, C6ꢁ), 27.0 and 26.6 [C(CH3)3], 19.3 and
19.2 [C(CH3)3].
Anal. calc. for: C86H94O11Si2 · H2O: C, 74.97; H, 7.02; found: C, 75.10; H,
7.31%.
1,2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-benzyl-6-O-(tert-butyldiphenylsilyl)
sucrose (16)
Disilylated derivative 14 (2.84 g, 2.1 mmol) was dissolved in THF (20 mL),
to which tetrabutylamonium fluoride trihydrate (1 g, 3.2 mmol) was added, and
the mixture was stirred at rt for 36 h and partitioned between water (20 mL)
and ethyl acetate (20 mL). The organic phase was separated and the aqueous
one extracted with ethyl acetate (3 × 20 mL). Combined organic solutions were
dried and concentrated, and the product was purified by column chromatogra-
phy (hexane/ethyl acetate, 8:1) to afford 16 (having very different polarity than
15, ꢀRf ∼ 0.5) as a colorless oil (1.36 g, 1.2 mmol, 66%).
[α]D = 29.8; m/z 1143.5105 calc. for [C70H76O11NaSi (M+Na): 1143.5049];
1H NMR (500 MHz) δ: 5.57 (d, 1H, J1,2 = 3.4 Hz, H-1), 1.07 [s, 9H, C(CH3)3];
13C NMR δ: 138.7, 138.5, 138.3, 138.25, 138.15, 137.8 (6 × Cquat. O CH2 Ph),
133.6 and 133.2 (2 × Cquat. Si Ph), 103.9 (C-2ꢁ), 91.2 (C-1), 83.6, 81.7, 81.3,
80.0, 79.9, 77.2, 72.6, (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4, C-2, C-5), 75.7, 75.0, 73.5, 73.2,
72.9, 72.5, 71.1 (6 × O CH2 Ph, C-1ꢁ), 62.0, 61.6 (C-6, C6ꢁ), 26.9 [C(CH3)3],
19.3 [C(CH3)3].
Anal. calc. for C70H76O11Si: C, 74.97; H, 6.83; found: C, 74.94; H, 6.74%.
6-O-Mesyl-6ꢀ-O-(tert-butyl-diphenylsilyl)-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-
benzylsucrose (17)
To a cooled (to 0◦C) solution of derivative 15 (1.08 g, 1 mmol) in dry methy-
lene chloride (20 mL) containing DMAP (20 mg) and triethylamine (0.5 mL,
3.6 mmol), mesyl chloride (0.2 mL, 2.6 mmol) was added dropwise, and the
mixture was stirred for 16 h at rt. Then water (20 mL) was added, the or-
ganic phase was separated, and the aqueous one extracted with ethyl acetate
(3 × 20 mL). Combined organic solutions were dried and concentrated, and the
product was purified by column chromatography (hexane/ethyl acetate, 5:1) to
afford 17 as a colorless oil (1.01 g, 0.8 mmol, 87%).
[α]D = 35.0; m/z 1221.4882 calc. for [C71H78O13SiSNa (M+Na): 1221.4825];
1H NMR (500 MHz) δ: 5.90 (d, 1H, J1,2 = 3.7 Hz, H-1), 4.08 (dt, 1H, J5,4 = 10.2
Hz, J5,6 = 2.4 Hz; H-5), 3.91 (d, 2H, H-6), 3.89 (dd, 1H, J3,2 = 9.4 Hz, J3,4
=
9.0 Hz, H-3), 3.47 (dd, 1H, H-4), 3.42 (dd, 1H, H-2), 2.68 (s, 3H, SO2CH3), 1.05
[s, 9H, C(CH3)3]; 13C NMR δ: 138.8, 138.3, 138.2 (double intensity), 137.9 and
137.8 (6 × Cquat. O CH2 Ph), 133.2 and 132.9 (2 × Cquat. Si Ph), 104.3 (C-2ꢁ),
88.8, 84.0, 81.8, 81.0, 80.6, 79.9, 76.8, 68.9 (C-1,C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2, C-3, C-4,

A. Gaweł & S. Jarosz
342
C-5), 75.5, 74.8, 73.5, 73.4, 72.7, 72.1, 72.0, 68.3, 63.8 (6 × O CH2 Ph, C-1ꢁ,
C-6, C6ꢁ), 36.9 (SO2CH3), 26.9 [C(CH3)3], 19.2 [C(CH3)3].
Anal. calc. for C71H78O13SSi: C, 71.09; H, 6.55; S, 2.67; found: C, 70.98; H,
6.60; S, 2.80%.
6-O-(tert-Butyl-diphenylsilyl)-6ꢀ-O-mesyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-
benzylsucrose (18)
To a cooled (to 0◦C) solution of derivative 16 (1.2 g, 1.1 mmol) in dry methy-
lene chloride (20 mL) containing DMAP (cat.) and triethylamine (0.5 mL, 3.6
mmol), mesyl chloride (0.2 mL, 2.6 mmol) was added dropwise, and the mixture
was stirred for 16 h at rt. Then water (20 mL) was added and reaction mixture
was partitioned between two phases; the organic one was collected and the
water one washed with ethyl acetate (3 × 20 mL). Combined organic phases
were dried and concentrated. Product was purified by column chromatography
(hexane/ethyl acetate, 5:1) to afford 18 as a colorless oil (1.2 g, 1.0 mmol, 93%).
[α]D = 29.1; m/z 1221.4725 calc. for [C71H78O13NaSSi (M+Na): 1221.4825];
1H NMR (600 MHz) δ: 5.75 (d, 1H, J1,2 = 3.0 Hz, H-1), 2.76 [s, 3H, S(O)2CH3];
13C NMR δ: 138.8, 138.6, 138.4, 137.74, 137.66, 137.6 (6 × Cquat. O CH2 Ph),
133.5 and 133.3 (2 × Cquat. Si Ph), 105.0 (C-2ꢁ), 90.5 (C-1), 83.9, 82.0, 81.9,
80.1, 78.2, 77.3, 72.0 (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4, C-2, C-5), 75.8, 74.9, 73.4,
73.1, 72.64, 72.59, 70.7, 69.9 (6 × O CH2 Ph, C-1ꢁ, C-6ꢁ), 62.6 (C-6), 37.3
[S(O)2CH3].
Anal. calc. for C71H78O13SSi · H2O: C, 70.04; H, 6.62; found: C, 70.16; H,
6.37%.
6-Iodo-6-deoxy-6ꢀ-O-(tert-butyl-diphenylsilyl)-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-
O-benzylsucrose (19)
To a solution of derivative 17 (0.79 g, 0.66 mmol) in DMF (10 mL), KI
(2 g) was added, and the mixture was stirred at 120◦C for 72 h. Then it was
cooled to rt and partitioned between water (10 mL) and diethyl ether (20 mL).
The organic phase was separated and the aqueous one extracted with ether
(3 × 40 mL). Combined organic solutions were dried and concentrated, and the
product was purified by column chromatography (hexane/ethyl acetate, 6:1) to
afford 19 as a colorless oil (0.72 g, 0.58 mol, 89%).
[α]D = 30.4; m/z 1253.4064 calc. for [C70H75O10NaSiI (M+Na): 1253.4066];
1H NMR (500 MHz) δ: 5.83 (d, 1H, J = 3.4 Hz, H-1); 13C NMR δ: 138.8, 138.7,
138.4, 138.2 and 137.9 double intensity (6 × Cquat. O CH2 Ph), 133.3 and
132.9 (2 × Cquat. Si Ph), 104.2 (C-2ꢁ), 88.8, 83.9, 81.54, 81.51, 80.9, 80.6, 80.2,
68.4 (C-1, C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2, C-3, C-4, C-5), 75.5, 75.0, 73.5, 73.4, 72.6, 72.1
double intensity and 63.8 (6 × O CH2 Ph, C-1ꢁ, C-6ꢁ), 27.0 [C(CH3)3], 19.2
[C(CH3)3], 10.3 (C-6).

Synthesis of Phosphorylated Derivatives of Sucrose
343
Anal. calc. for C70H75IO10Si: C, 68.28; H, 6.14; I, 10.31; found: C, 68.42; H,
6.37; I, 10.36%.
6-O-(tert-Butyl-diphenylsilyl)-6ꢀ-deoxy-6ꢀ-iodo-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-
O-benzylsucrose (20)
To a solution of derivative 18 (1.07 g, 0.9 mmol) in DMF (10 mL), KI (3 g)
was added, and the mixture was stirred at 120◦C for 72 h. Then it was cooled
to rt and partitioned between water (10 mL) and diethyl ether (20 mL). The
organic phase was separated and the aqueous one extracted with ether (3 × 40
mL). Combined organic solutions were dried and concentrated, and the product
was purified by column chromatography (hexane/ethyl acetate, 6:1) to afford 20
as a colorless oil (0.48 g, 0.4 mmol, 44%).
[α]D = 21.5; m/z 1253.4025 calc. for [C70H75O10NaSiI(M+Na): 1253.4066];
1H NMR (600 MHz) δ: 5.64 (d, 1H, J1,2 = 3.5 Hz, H-1), 1.07 [s, 9H, C(CH3)3];
13C NMR δ: 138.79, 138.75, 138.4, 138.0, 137.9, 137.8 (6 × Cquat. O CH2 Ph),
133.6 and 133.3 (2 × Cquat. Si Ph), 104.8 (C-2ꢁ), 90.3 (C-1), 85.3, 84.5, 81.9,
80.4, 80.3, 77.4, 72.0 (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4, C-2, C-5), 75.7, 74.9, 73.3,
72.83, 72.76, 72.4, 71.1, 62.6 (6 × O CH2 Ph, C-1ꢁ, C-6), 26.9 [C(CH3)3], 19.3
[C(CH3)3], 6.4 (C-6ꢁ).
Anal. calc. for C70H75IO10Si: C, 68.28; H, 6.14; found: C, 68.39; H, 6.05%.
6-(Diethoxy-phosphoryl)-6-deoxy-6ꢀ-O-(tert-butyl-diphenylsilyl)-
1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzylsucrose (21)
Compound 19 (0.59 g, 0.48 mmol) was dissolved in P(OEt)3 (5 mL) and
stirred and boiled under reflux in the oxygen-free atmosphere for 72 h. Excess
of P(OEt)3 was evaporated (below 70◦C) and the product was purified by col-
umn chromatography (hexane/ethyl acetate, 3:1) to afford 21 as a colorless oil
(0.51 g, 0.41 mmol, 86%).
[α]D
= 24.3; m/z 1263.5396 calc. for [C74H85O13NaSiP (M+Na):
1
1263.5389]; H NMR (500 MHz) δ: 5.67 (d, 1H, J1,2 = 3.6 Hz; H-1), 3.82–3.92
(m, 4H, P O CH2 CH3); 31P NMR δ: 29.91; 13C NMR δ: 138.8, 138.7, 138.42,
138.40, 138.21 and 138.18 (6 × Cquat. O CH2 Ph), 133.5 and 133.3 (2 × Cquat.
Si Ph), 105.0 (C-2ꢁ), 90.5 (C-1), 84.5, 83.7 and 81.9, 66.8 (d, JCP = 7.4 Hz) (C-
3ꢁ, C-4ꢁ, C-5, C-5ꢁ), 81.7 (C-3), 80.9 (d, JCP = 9.1 Hz; C-4), 80.1 (C-2), 75.3, 74.7,
73.4, 73.2, 72.4, 72.2, 70.5 (6 × O CH2 Ph, C-1ꢁ), 66.0, 61.3 (d, JCP = 6.1 Hz),
61.2 (d, JCP = 6.2 Hz) (2 × P O CH2 CH3, C-6, C-6ꢁ), 28.5 (d, JCP = 98.7
Hz) and 23.4 (d, JCP = 99,2 Hz; 2 × P O CH2 CH3), 26.9 [C(CH3)3], 19.2
[C(CH3)3].
Anal. calc. for C74H85O13Psi · H2O: C, 70.56; H, 6.96; found: C, 70.13; H,
7.33%.

A. Gaweł & S. Jarosz
344
1,2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-benzyl-6-deoxy-6-(diethoxyphoshonate)
sucrose (21a)
Compound 21 (245 mg, 0.20 mmol) was dissolved in THF (5 mL) containing
tetrabutylamonium fluoride trihydrate (75 mg, 0.24 mmol), and the mixture
was stirred at 60◦C for 6 h, cooled to rt, and concentrated. Column chromatog-
raphy (hexane/ethyl acetate, 3:1 to 1:1) afforded 21a (146 mg, 0.14 mmol, 74%)
as a colorless oil.
[α]D = 29.7 (c = 0.35); m/z 1025.4160 calc. for [C58H67O13NaP (M+Na):
1
1025.4212]; H NMR (500 MHz) δ: 5.59 (d, 1H, J1,2 = 3.4 Hz, H-1); 31P NMR
δ: 29.89; 13C NMR δ: 138.7, 138.6, 138.4, 138.3, 138.1 and 137.7 (6 × Cquat.
O CH2 Ph), 104.2 (C-2ꢁ), 90.8 (C-1), 84.4, 81.5, 81.4, 81.3, 81.2, 79.9 and
67.2 (d, JCP = 6.6 Hz) (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4, C-2, C-5), 75.3, 74.8, 73.5,
72.9, 72.7, 72.5, 70.5, 62.3, 61.6 (m) (6 × O CH2 Ph, C-1ꢁ, C-6, C-6ꢁ, 2 ×
P O CH2 CH3), 16.4 (m) (2 × P O CH2 CH3).
Anal. calc. for C58H67O13P · 2H2O: C, 67.01; H, 6.89; found: C, 66.75; H,
6.88%.
6ꢀ-(Diethoxy-phosphoryl)-6ꢀ-deoxy-6-O-(tert-butyldiphenylsilyl)-
1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzylsucrose (22)
Compound 20 (0.40 g, 0.32 mmol) was dissolved in P(OEt)3 (5 mL) and
stirred at 120◦C in the oxygen-free atmosphere for 72 h. The excess of P(OEt)3
was evaporated (below 70◦C) and the product was purified by column chro-
matography (hexane/ethyl acetate, 3:1) to afford 22 as a colorless oil (0.18 g,
0.14 mmol, 45%).
[α]D
= 28.2; m/z 1263.5441 calc. for [C74H85O13NaSiP (M+Na):
1263.5389]; 1H NMR (500 MHz;) δ: 5.68 (d, 1H, J1,2 = 3.3 Hz, H-1); 31P
NMR δ: 28.9; 13C NMR δ: 138.9, 138.8, 138.4, 138.10, 138.06, 138.0 (6 × Cquat.
O CH2 Ph), 133.6 and 133.3 (2 × Cquat. Si Ph), 104.9 (C-2ꢁ), 90.0 (C-1), 85.6
(d, JCP = 12.5 Hz), 83.7, 82.1, 80.3, 77.4, 75.5, 71.9 (C-3ꢁ, C-4ꢁ, C-5ꢁ, C-3, C-4,
C-2, C-5), 75.7, 74.8, 73.4, 72.8, 72.5, 72.3, 71.6, 62.6, 61.7 (d, JCP = 6.1 Hz),
61.4 (d, JCP = 5.6 Hz) (6 × O CH2 Ph, C-1ꢁ, C-6ꢁ, C-6, 2 × P O CH2 CH3),
26.9 [C(CH3)3], 19.3 [C(CH3)3], 16.4 (m) (2 × P O CH2 CH3).
Anal. calc. for C74H85O13SiP · 2H2O: C, 69.57; H, 7.02; found: C, 69.38; H,
7.02%.
1,2,2ꢀ,3,3ꢀ,4,4ꢀ-Hexa-O-benzyl-6ꢀ-deoxy-6ꢀ-(diethoxyphoshonate)
sucrose (22a)
Compound 22 (140 mg, 0.11 mmol) was treated analogously (to 21) with
tetrabutylamonium fluoride trihydrate without any result. We could observe

Synthesis of Phosphorylated Derivatives of Sucrose
345
formation of 22a only with tetrabutylamonium fluoride trihydrate in the pres-
ence of KOH and methanol, but the product was formed in very small amounts
detectable by ms: m/z 1025 [M(C78H76O9P2)+Na+].
6,6ꢀ-bis-(Diphenylphosphino)-6,6ꢀ-dideoxy-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-
benzylsucrose (23)
To a solution of triphenyl phosphine (0.86 g, 3.3 mmol) in dry THF (25 mL),
metallic sodium (0.15 g, 6.5 mmol) was added in small pieces and the mixture
was stirred at rt for 24 h under oxygen-free atmosphere (colorless solution
became deep red). Such deeply red solution of phosphide was transferred via
syringe into the solution of the dichloride derivative 9 (1 g, 1.1 mmol) in THF
(5 mL) under oxygen-free atmosphere and the mixture was stirred at rt for
48 h (discoloration of the mixture). The residue was partitioned between water
(15 mL) and toluene (15 mL), the organic phase was separated, and the aque-
ous one was extracted with toluene (3 × 30 mL). Combined organic solutions
were dried and concentrated, and the residue was purified by column chro-
matography (hexane/ethyl acetate, 4:1 to 3:1) to afford 23 (0.39 g, 0.32 mmol,
29%) as a colorless oil.
Significant amounts of the di-oxide 24 were also isolated (hexane-ethyl ac-
etate, 2:1 to 1:1).
1
Data for 23: m/z 1219 [M(C78H76O9P2)+H+]; H NMR (400 MHz) δ: 5.51
(d, 1H, J1,2 = 3.3 Hz, H-1); 31P NMR δ: −22.1, −24.8; 13C NMR δ: 138.8, 138.7,
138.5, 138.4, 138.3, 138.1 (6 × C Cquat. O CH2 Ph), 104.4 (C-2ꢁ), 89.6, 86.6
(m), 84.2, 82.8 (d, JCP = 9,4 Hz), 81.7, 80.2 and 78.6 (d, JCP = 16,3 Hz) (C-1,
C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2, C-3, C-4), 75.4. 74.9, 73.2, 72.5 (m), 72.4, 71.4 and 65.8 (C-
1ꢁ, 6 × O CH2 Ph), 69.4 (d, JCP = 13,7 Hz, C-5), 34.2 (m) and 32.4 (d, JCP
=
14,6 Hz, C-6ꢁ and C-6).
Data for 24: [α]D = 3.6; m/z 1273.4728 calc. for [C78H76O11NaP2 (M+Na):
1
1273.4755] H NMR (400 MHz) δ: 5.04 (d, 1H, J1,2 = 3.3 Hz, H-1); 31P NMR
δ: 29.27, 28.0; 13C NMR δ: 138.60 double intensity, 138.57, 138.4, 138.2, 138.0
(6 × Cquat. O CH2 Ph), 105.1 (C-2ꢁ), 89.9, 85.9 (d, JCP = 8.6 Hz), 83.8, 81.9 (d,
JCP = 9.4 Hz), 81.3, 79.9 and 75.7 (d, JCP = 2.5 Hz) (C-1, C-3ꢁ, C-4ꢁ, C-5ꢁ, C-2,
C-3, C-4), 75.2, 74.7, 73.3, 72.4, 72.3, 72.1 and 70.7 (6 × O CH2 Ph, C-1ꢁ),
67.0 (d, JCP = 5.1 Hz, C-5), 35.3 (d, JCP = 69.4 Hz) and 32.0 (d, JCP = 72.8 Hz,
C-6ꢁ, C-6).
Anal. calc. for C78H76O11P2: C, 74.86; H, 6.12; found: C, 74.88; H, 6.14%.
The di-oxide 24 was converted into di-phosphine 23 by reduction with
LAH. Thus, derivative 24 (185 mg, 0.15 mmol) was dissolved in THF (5 mL)
containing methyl iodide (0.03 mL, 0.48 mmol) and the mixture was stirred un-
der oxygen-free atmosphere at rt for 10 min. LAH (45 mg, 1.2 mmol) was added
and stirring was prolonged for another 24 h. Methanol (1 mL) was added and
the mixture was partitioned between water (10 mL) and ethyl acetate (20 mL).

A. Gaweł & S. Jarosz
346
The organic phase was separated and the aqueous one extracted with ethyl
acetate (2 × 20 mL). Combined organic solutions were dried and concentrated,
and the product was isolated by column chromatography (hexane/ethyl acetate,
4:1 to 3:1) to afford 23 as a colorless foam (88 mg, 0.07 mmol, 49%).
6,6ꢀ-bis-(Diphenylphosphinyl)-6,6ꢀ-dideoxy-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-
benzyl-sucrose (24)
A mixture of 23 and 24 (isolated from the preparation of phosphine 23 from
9; 0.2 g, 0.22 mmol) was dissolved in acetone (3 mL), to which hydrogen perox-
ide (30% in water, 0.2 mL) was added, and the mixture was stirred for 24 h at
rt. Then it was partitioned between water (5 mL) and ethyl acetate (15 mL).
The organic phase was separated and the aqueous one extracted with ethyl ac-
etate (3 × 15 mL). Combined organic solutions were dried and concentrated to
afford title 24 in quantitative yield identical in all respects with the previously
prepared sample.
ACKNOWLEDGEMENT
The support from grant POIG.01.01.02-14-102/09 (part-financed by the
European Union within the European Regional Development Fund) is
acknowledged.
Selective desilylation at the “fructose part” was observed previously by us
for similar sucrose derivatives (see ref. 2).
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