Sucrose analogs containing sulfur functionalities

Article abstract of DOI:10.1080/10426500902856370

Regioselective synthesis of sucrose monosulfides, with sulfur functionality placed either at the C-6 (glucose part) or C-6′ (fructose) ends, is presented. The performed model dimerization of the mercaptane into the disulfide opens a convenient route to th

Full text of DOI:10.1080/10426500902856370

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Phosphorus, Sulfur, and Silicon
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Sucrose Analogs Containing
Sulfur Functionalities
Slawomir Jarosz a , Arkadiusz Listkowski a & Bartosz
Lewandowski a
a Institute of Organic Chemistry , Polish Academy of
Sciences , Warsaw, Poland
Published online: 28 Apr 2009.
To cite this article: Slawomir Jarosz , Arkadiusz Listkowski & Bartosz
Lewandowski (2009) Sucrose Analogs Containing Sulfur Functionalities,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:5, 1285-1295, DOI:
10.1080/10426500902856370
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Phosphorus, Sulfur, and Silicon, 184:1285–1295, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902856370
Sucrose Analogs Containing Sulfur Functionalities
Slawomir Jarosz, Arkadiusz Listkowski,
and Bartosz Lewandowski
Institute of Organic Chemistry, Polish Academy of Sciences,
Warsaw, Poland
Regioselective synthesis of sucrose monosulfides, with sulfur functionality placed
either at the C-6 (glucose part) or C-6ꢀ (fructose) ends, is presented. The performed
model dimerization of the mercaptane into the disulfide opens a convenient route
to the open-chain sucrose dimers.
Keywords Carbohydrates; sucrose disulfides; sucrose thiols
INTRODUCTION
Sucrose (β-D-fructofuranosyl α-D-glucopyranoside, 1) is by far the most
widely available low-weight carbohydrate. The overall production of
this disaccharide in 2006 equals to 150 million tons; most of it is con-
sumed on the food market. Nevertheless, a lot of work is performed to
utilize this cheap raw material in other fields; the research on surfac-
tants, emulsifiers, biodegrading polymers, or liquid crystals with the
sucrose scaffold is intensively pursued.1
As a part of an ongoing program aimed at modification of sucrose
with the preservation of the disaccharide skeleton, we have elaborated
a convenient route to 2,3,3ꢀ,4,4ꢀ-penta-O-benzyl-sucrose (2), which al-
lowed modification of this disaccharide at any of the terminal positions:
C-1ꢀ, C-6, and C-6ꢀ (Figure 1).2
Especially interesting, however, was another derivative,
1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzyl-sucrose (3),3 which served as a useful
precursor of macrocyclic receptors of type 4 with the sucrose scaf-
fold. Different types of such macrocycles (X = O, N) were prepared
(Figure 2).4
Received 12 January 2008; accepted 28 January 2008.
Dedicated to Professor Marian Mikolajczyk, CBMiM PAN in Lo´dz´, Poland, on the
ꢀ
ꢀ
occasion of his 70th birthday.
Address correspondence to Slawomir Jarosz, Institute of Organic Chemistry, Polish
Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland. E-mail: sljar@icho.edu.pl
1285

1286
S. Jarosz et al.
FIGURE 1 Penta-O-benzylsucrose and its modifications at the terminal posi-
tions.
An interesting approach consists of the synthesis of sulfur deriva-
tives of sucrose, which may serve as convenient precursors of macro-
cycles with higher symmetry built on the carbohydrate scaffold. Re-
cently, dithiol 5 has been prepared from diol 33; we have found that
this compound can be oxidized (I2) to the disulfide 6, which, after re-
duction (LiAlH4), can be converted back into the initial dimercaptane 53
(Figure 3).
RESULTS AND DISCUSSION
The process shown in Figure 3 allows us to obtain the “monomeric”
sucrose macrocyles. (Formation of such disulfides from free sucrose
was described in ref.5) In this article, we would like to propose another
approach that may provide sucrose macrocycles with higher symmetry.
This work is aimed, therefore, at the synthesis of the building blocks
that should serve as starting materials in a macrocyclization process.
FIGURE 2 Hexa-O-benzylsucrose and its conversion into the macrocyclic re-
ceptors.

Sucrose Analogs Containing Sulfur Functionalities
1287
FIGURE 3 Synthesis of sucrose di-mercaptane and its cyclization.
The idea is outlined in Figure 4. Properly substituted sucrose mono-
sulfides (e.g., 7 or 8) can be oxidized to a disulfide in which the remain-
ing primary positions are susceptible for the (eventual) coupling. After
such coupling (which may be done on several routes), the C-2 symmetri-
cal macrocyclic disulfides with the sucrose scaffold should be obtained.
Another approach to the same macrocycles consists of coupling of the
non-sulfated positions first, followed by oxidation of the dimercaptane.
Nevertheless, in both cases a convenient and simple route leading
to sucrose mono-mercaptanes is required. In this communication, the
synthesis of the monothiols of type 7 and 8 with the mercapto group
placed at either terminal position (C-6 or C-6ꢀ) will be presented, as
well as the approach of dimerization of these valuable synthons.
The first route started from 6ꢀ-O-(tbutyldiphenylsilyl)-hexa-O-
benzylsucrose6 9, which is readily available from the parent diol 3.
Standard transformations involving activation of the remaining pri-
mary 6-OH (at the glucose part) as mesylate 10, followed by reaction
with the SH− anion, provided the protected mercaptane 11 in good
overall yield (Scheme 1). To prepare the alternative C-6ꢀ mercaptane,
FIGURE 4 A route to sulfur macrocycles with the sucrose scaffold.

1288
S. Jarosz et al.
SCHEME 1 i. ref. 6; ii. MsCl, DMAP, CH2Cl2/NEt3, 95%; iii. NaSHxnH2O,
DMF, 56%; iv. ClCH2CN, toluene, 50% NaOH, 65%; v. AcSH, DBU, DMF, 60%
we took advantage of the different reactivity of both terminal hy-
droxyl groups in sucrose 3. We have observed that the reactivity of
the “glucose” hydroxyl group towards C-nucleophiles is much higher
than the reactivity of the “fructose” (6ꢀ-OH) one. Reaction of the diol
3 with chloroacetonitrile under the PTC conditions7 afforded the 6-O-
protected derivative 12. The position of the substitution was proven
unambiguously by the chemical and spectral correlation. The Swern
oxidation8 of the free hydroxyl group in 12 followed by reaction with
Ph3P=CHCO2Me afforded the α,β-unsaturated ester 14. The resonance
of the H-5ꢀ proton was shifted downfield by ∼ 0.3 ppm (from δ ∼ 4.10
ppm for 12 to δ = 4.40–4.45 ppm for 14), thus proving that unsaturation
is located at the fructose part, hence the reaction of chloroacetonitrile
occurred at the 6-OH (glucose) hydroxyl group.

Sucrose Analogs Containing Sulfur Functionalities
1289
Standard transformations of 12 (mesylation followed by reac-
tion with thioacetate anion) provided derivative 13 in good yield
(Scheme 1).
Application of the mono-thiols to the synthesis of dimeric sucrose
derivatives is shown in Scheme 2. Oxidation of the mercaptane 11 with
iodine led to the C2-symmetrical disulfide 15 in good yield. Its structure
was proven by the MS and NMR data (see the Experimental section).
The silyl protecting groups were easily removed with the fluoride anion
providing the diol 16 (Scheme 2).
SCHEME 2 i. benzene, 20% NaOH, I2, 86%.
The alternative compound could be, eventually, prepared from the
protected thiol 13 by its methanolysis (to 17) followed by oxidation to
disulfide with iodine. These results will be reported in due course.
CONCLUSION
The convenient approach to sucrose-based monothiols from the readily
available hexa-O-benzylsucrose is reported. Oxidation of the monosul-
fide to the disulfide is conveniently achieved with iodine in basic media.
The proposed route opens an interesting way to the macrocyclic recep-
tors with the sucrose scaffold. This may be achieved by coupling of the
remaining positions (such as, e.g., both C-6ꢀ positions in compound 16,
which can be performed by a variety of methods). Further study is in
progress.

1290
S. Jarosz et al.
EXPERIMENTAL
General
1H and 13C NMR spectra were recorded with a Varian Gemini 200
MHz or a Bruker AM 500 MHz spectrometer for solutions in CDCl3
(internal Me4Si). Mass spectra (ESI) were recorded with a Mariner PE
Biosystem apparatus. Most of the resonances were identified by the
1
1H-1H and H-13C NMR correlations. The aromatic signals occurring
1
at the typical δ values (in 13C and H NMR) were omitted for simplic-
ity. Optical rotations were measured with JASCO Polarimeter P-1020
(sodium lamp λ = 589 nm) for solutions in chloroform at room temper-
ature for c = 1. Column chromatography was performed on silica gel
(Merck, 70–230 or 230–400 mesh). All solutions were dried over an-
hydrous magnesium or sodium sulfate. The solvents were evaporated
under diminished pressure.
6-O-Mesyl-6ꢀ-O-tert-butyldiphenylsilyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-
hexa-O-benzylsucrose (10)
6ꢀ-O-tert-butyldiphenylsilyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzylsucrose (9,
0.343 g, 0.31 mmol) was dissolved in anhydrous CH2Cl2 (15 mL), to
which triethylamine (2 mL) and DMAP (20 mg) were added. Mesyl
chloride (0.3 mL) was added slowly; the reaction mixture was stirred
at room temperature for 0.5 h and diluted with CH2Cl2 (25 mL). Water
(25 mL) was added, the organic phase was separated and washed with
water (20 mL), and the aqueous one extracted with CH2Cl2 (25 mL).
Combined organic phases were dried, concentrated, and the product
was isolated by column chromatography (hexane:ethyl acetate, 4:1) to
give the title compound 10 (0.354 g, 0.295 mmol, 95%) as a colorless
oil. [α]D = +32.7, MS (ESI) m/z = 1221.2 [(C71H78O13SSi)+Na+]; IR
(νcm−1): 3031, 2930, 2859, 1454, 1361, 1177, 1090, 1027, 1004, 737,
698, 504. 1H NMR (500 MHz): δ = 5.90 (d, J1,2 = 3.7 Hz, 1H, H-1),
4.87 (d, J = 10.9 Hz, 1H), 4.86 (d, J = 10.9 Hz, 1H), 4.70–4.63 (m,
4H), 4.62 (d, J = 1.6 Hz, 1H), 4.58–4.37 (m, 7H), 4.08 (ddd, J = 2.5,
J = 2.5, J = 10.3 Hz, 1H, H-5 or H-5ꢀ), 4.02–3.95 (m, 2H), 3.92–3.81
(m, 4H), 3.69 (d, J = 10.9 Hz, 1H), 3.55 (d, J = 10.9 Hz, 1H), 3.47 (dd,
J = 8.9, J = 10.2 Hz, 1H), 3.42 (dd, J2,3 = 9.6 Hz, 1H, H-2), 2.68 (s,
3H, OSO2CH3), 1.05 (s, 9H, CMe3); 13C NMR (125 MHz): δ = 137.9,
137.8 (Cquart benzyl), 135.7, 135.5 (phenyl-C from TBDPS), 133.2,
132.9 (Cquart phenyl from TBDPS), 129.81, 129.77 (phenyl-C from
TBDPS), 104.3 (C-2ꢀ), 88.8 (C-1), 84.0, 81.9, 81.0, 80.6, 79.9, 76.8 and
ꢀ
68.9 (C-2,3,3ꢀ,4,4, 5,5ꢀ), 75.5, 74.8, 73.5, 72.7, 72.14, 72.06 and 68.3,
63.8 (CH2Ph, C-1ꢀ,6,6ꢀ), 37.0 (OSO2CH3), 26.9 (CMe3), 19.3 (CMe3).

Sucrose Analogs Containing Sulfur Functionalities
1291
6-Deoxy-6-thio-6ꢀ-O-tert-butyldiphenylsilyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-
hexa-O-benzylsucrose (11)
The mesylate 10 was dissolved in DMF (20 mL) to which NaSH ×
n H2O (0.3 g) was added; the mixture was stirred at room tempera-
ture overnight and then partitioned between water (40 mL) and ether
(40 mL). The water phase was extracted with ether (50 mL) and dis-
carded. Combined organic phases were dried, concentrated, and the
expected product was isolated from the more polar impurities by col-
umn chromatography (hexane:ethyl acetate, 12:1 to 6:1) as a colorless
oil (0.214 g, 0.188 mmol, 56%). [α]D = +37.1; MS (ESI) m/z = 1159.3
[(C70H76O10SSi)+Na+]; IR (νcm−1): 3030, 2931, 2862, 1455, 1087, 1026,
737, 698, 504. 1H NMR (500 MHz): δ = 5.85 (d, J1,2 = 3.6 Hz, 1H, H-1),
4.87 (d, JA,B = 11.2 1H, Hz), 4.85 (d, JA,B = 10.7 Hz, 1H), 4.69–4.43 (m,
12H), 4.38 (dd, J = 7.6, J = 7.7 Hz, 1H), 4.05 (ddd, J = 3.6, J = 3.6,
J = 9.8 Hz, 1H, H-5 or H-5ꢀ), 4.02–3.95 (m, 2H), 3.90 (dd, J = 9.6,
J = 9.6 Hz, 1H) 3.88–3.83 (m, 1H), 3.69 (d, JA,B = 11.0 Hz, 1H, H-
1ꢀA), 3.61 (dd, J = 9.4, J = 9.4 Hz, 1H), 3.56 (d, 1H, H-1ꢀB), 3.42 (dd,
J2,3 = 9.6 Hz, 1H, H-2), 2.61–2.55 (m, 1H, H6A), 2.36–2.29 (m, 1H,
H6B), 1.06 (s, 9H, CMe3); 13C NMR (125 MHz): δ = 138.9, 138.7, 138.4,
138.2, 138.1, 138.0 (Cquart benzyl), 135.7, 135.5 (phenyl-C from TBDPS),
133.2, 133.0 (Cquart phenyl from TBDPS), 129.74, 129.69 (phenyl-C from
TBDPS), 104.3 (C-2ꢀ), 89.0 (C-1), 83.9, 81.8, 81.2, 80.8, 80.3, 78.4, and
70.0 (C-2,3,3ꢀ,4,4, ꢀ,5,5ꢀ), 75.5, 74.7, 73.5, 73.2, 72.6, 72.2, 72.0 and 64.2
(CH2Ph, C-1ꢀ,6ꢀ), 26.9 (CMe3), 26.1 (C-6), 19.3 (CMe3). Anal. Calcd for
C70H76O10SSi: C, 73.91, H, 6.73; S, 2.82. Found: C, 73.8; H, 6.7; S, 2.7%.
6-O-(Cyanomethyl)-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzylsucrose (12)
1ꢀ,2,3,3ꢀ,4,4ꢀ-Hexa-O-benzylsucrose 3 (340 mg, 0.38 mmol) was dis-
solved in toluene (5 mL), to which 50% aqueous NaOH (5 mL) and tetra-
butylammonium bromide (5 mg) were added. A solution of chloroace-
tonitrile (0.05 mL) in toluene (10 mL) was then added dropwise during
30 min, and the mixture was stirred vigorously for additional 2 h. Wa-
ter (15 mL) was added, the layers were separated, and the aqueous
one extracted with ethyl acetate (2 × 15 mL). Combined organic layers
were washed with water (15 mL) and brine (15 mL), and dried. The
solution was filtered and concentrated, and the product was isolated
by column chromatography (hexane:ethyl acetate, 3:1) as a yellowish
oil (230 mg, 0.25 mmol, 66%). HR MS (ESI) m/z: 944.3990; [calcd. for
(C56H59NO11Na (M + Na+): 944.3980]; 1H NMR (500 MHz): δ = 5.51 (d,
J1,2 = 3.4 Hz, 1H, H-1). 13C NMR (125 MHz): δ = 138.6, 138.19, 138.15,
138.07, 138.0, 137.8 (Cquart benzyl), 115.8 (CN), 103.9 (C-2ꢀ), 90.9

1292
S. Jarosz et al.
(C-1); 83.7, 81.7, 81.2, 79.4, 79.3, 76.8, 70.8 (C-2,3,3ꢀ,4,4ꢀ,5,5ꢀ), 75.6,
75.1, 73.44, 73.37, 72.8, 72.6, 71.4, 69.7, 69.6 (OCH2Ph, C-6,1ꢀ,6ꢀ).
Determination of the Structure of 12; Synthesis of Olefin 14
To a cooled to −70◦C solution of oxalyl chloride (0.04 mL) in dry
dichloromethane (10 mL), a solution of DMSO (0.13 mL) in CH2Cl2 (0.5
mL) was added dropwise, followed by a solution of 12 (120 mg, 0.13
mmol) in dry CH2Cl2 (2 mL). The mixture was stirred at −70◦C for 30
min, and then triethylamine (0.13 mL) was added. Stirring was con-
tinued for 1 h at −70◦C, and the solution was allowed to warm to room
temperature. Water (10 mL) was added, and the organic phase was
separated, dried, and filtered. Phosphonium ylide (Ph3P CHCO2Me,
126 mg, 0.35 mmol) was added, and the mixture was stirred at room
temperature until completion (30 min; TLC monitoring in hexane:ethyl
acetate, 3:1). Water (10 mL) was added; the layers were separated; the
organic one was washed with water (10 mL) and brine (10 mL), dried,
filtered, and concentrated; and the product was purified by column
chromatography (hexane:ethyl acetate, 5:1) to afford compound 14 as
colorless oil (85 mg, 0.087 mmol, 67% over 2 steps). 1H NMR (500 MHz):
δ = 7.03 (dd, J = 15.7, J = 6.7 Hz, 1H, Hβ), 6.07 (dd, J = 1.1 Hz, 1H,
Hα), 5.48 (d, J = 3.5 Hz, 1H, H-1), 4.51–4.92 (m, 10H, OCH2Ph), 4.40–
4.45 (m, 2H, H-5ꢀ+ H-3ꢀ), 4.35–4.38 (m, 2H, OCH2Ph), 4.08–4.14 (m,
3H, H-4ꢀ + OCH2CN), 4.02 (m, 2H, H-6), 3.96 (m, 1H, H-3), 3.73 (s,
3H, CO2CH3), 3.60–3.65 (m, 3H, H-1ꢀ + H-5), 3.48–3.52 (m, 2H, H-2
+ H-4). 13C NMR (125MHz): δ = 166.4 (CO2CH3), 145.5 (Cβ), 138.7,
138.2, 138.1, 137.9, 137.70, 137.68 (Cquart benzyl groups), 122.4 (Cα),
116.0 (CN), 104.7 (C2ꢀ), 90.2 (C-1), 84.3 (C-4ꢀ), 83.2 (C-3ꢀ), 81.9 (C-3),
79.5 (C-2), 79.1 (C-5ꢀ), 77.2 (C-4), 70.9 (C-5), 75.6, 75.0, 73.41, 72.98,
72.96, 72.94 (OCH2Ph), 70.5 (C-6), 69.8 (C-1ꢀ), 56.7 (OCH2CN), 51.5
(CO2CH3).
6-O-(Cyanomethyl)-6ꢀ-deoxy-6ꢀ-thioacetyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-
hexa-O-benzylsucrose (13): Synthesis of the Thioacetic Salts
DBU salt: DBU (0.03 mL, 0.2 mmol) was dissolved in DMF (5 mL).
Thioacetic acid (0.014 mL, 0.2 mmol) was added, and the mixture was
stirred for 3 min and used in the SN2 reaction.
Cesium salt: Cs2CO3 (65 mg, 0.2 mmol) was dissolved in methanol
(10 mL). Thioacetic acid (0.028 mL, 0.4 mmol) was added to the mixture,
and it was stirred for 3 min and then concentrated. The obtained yelow
solid was dissolved in DMF (5 mL) and used in the SN2 reaction.
Sucrose derivative 12 (210 mg, 0.22 mmol) was dissolved in
dichloromethane (10 mL) containing Et3N (2 mL) and DMAP (10 mg).

Sucrose Analogs Containing Sulfur Functionalities
1293
Mesyl chloride (0.2 mL) was added dropwise, and the mixture was
stirred at room temperature for 4 h and partitioned between water
(15 mL) and dichloromethane (10 mL). The layers were separated,
and the aqueous one extracted with diethyl ether (2 × 10 mL). The
combined organic layers were dried, filtered, and concentrated, and
the product was isolated by column chromatography (hexane:ethyl ac-
etate, 3:1) to give the corresponding mesylate as a yellowish oil (210
mg, 0.21 mmol, 95%). MS (ESI) m/z: 1022.2 [M(C57H61NO13S) + Na+];
1H NMR (500 MHz): δ = 5.53 (d, J = 3.6 Hz, 1H, H-1), 2.92 (s, 3H,
mesyl group). 13C NMR (125MHz): δ = 138.6, 138.06, 138.03, 137.91,
137.62, 137.61 (Cquart benzyl), 115.9 (CN), 104.9 (C-2ꢀ), 90.4 (C-1), 83.5,
81.8, 81.5, 79.6, 78.0, 77.2, 70.5 (C2,3,3ꢀ,4,4ꢀ,5,5ꢀ), 75.6, 75.0, 73.4, 73.0,
72.9, 72.6, 70.7, 70.1, 69.8 (OCH2Ph, C-6, C-1ꢀ, C-6ꢀ), 56.6 (OCH2CN),
37.3 (OSO2CH3).
This mesylate (50 mg, 0.05 mmol) was dissolved in DMF (5 mL),
to which a solution of DBU thioacetate (prepared according to pro-
cedure described above) was added, and the mixture was stirred at
80◦C for 2 days. Then the mixture was cooled to room temperature,
and partitioned between water (20 mL) and diethyl ether (20 mL).
The layers were separated and the aqueous one extracted with di-
ethyl ether (3 × 15 mL). The combined organic extracts were washed
with water (15 mL) and brine (15 mL), dried over magnesium sulfate,
filtered, and concentrated. The product was isolated by column chro-
matography (hexane:ethyl acetate, 4:1) to afford 13 as a yellow oil (30
mg, 0.031 mmole, 67%). Similar results were obtained with cesium
1
thioacetate. MS (ESI) m/z: 980.6 [M(C58H61NO11S) + H+]; H NMR
(500 MHz): 5.59 (d, J = 3.6 Hz, 1H, H-1), 1.99 (s, 3H, SAc). 13C NMR
(125 MHz): δ = 170.7 (SC(O)CH3); 138.8, 138.2, 138.1, 138.0, 137.9,
137.7 (Cquart benzyl), 115.9 (CN), 104.7 (C-2ꢀ), 90.0 (C-1), 83.7, 81.9,
81.8, 79.6, 78.2, 78.0, 70.3 (C-2,3,3ꢀ,4,4ꢀ,5,5ꢀ), 75.5, 75.0, 73.5, 73.0,
72.64, 72.55, 71.1, 70.0, 65.1 (OCH2Ph, C-6, C-1ꢀ, C-6ꢀ), 56.6 (OCH2CN),
20.8 (SC(O)CH3).
Bis-(6-deoxy-6ꢀ-O-tert-butyldiphenylsilyl-1ꢀ,2,3,3ꢀ,4,4ꢀ-
hexa-O-benzylsucros-6ꢀ-yl)-disulfide (15)
Monosulfide 11 (0.191 g, 0.168 mmol) was dissolved in benzene (10
mL), to which a solution of NaOH (0.152 g, 0.304 mmol) in water (0.5
mL) was added, followed by iodine (72 mg, 0.57 mmol). The mixture
was stirred for 3.5 h at room temperature, and then 20% aqueous so-
lution of NaOH was added until the color disappeared. Water (40 mL)
and ethyl acetate (40 mL) were added, and the organic phase was sep-
arated, washed with 20% aqueous solution of NaOH (40 mL), dried,

1294
S. Jarosz et al.
and concentrated. The product was isolated by column chromatogra-
phy (hexane:ethyl acetate, 8:1 to 6:1) to afford 15 (0.165 g, 0.0727
mmol, 86%) as a colorless oil. [α]D = +35.9; MS (ESI) m/z = 2295.9
1
[(C140H150O20S2Si2)+Na+]. H NMR (500 MHz): δ = 5.79 (d, J1,2 = 3.5
Hz, 1H, H-1), 4.79 (d, J = 11.3 Hz, 1H), 4.77 (d, J = 11.0 Hz, 1H), 4.66–
4.32 (m, 12 H), 4.13–4.08 (m, 1H), 4.04–3.87 (m, 3H), 3.82 (dd, J = 9.2,
J = 9.2 Hz, 1H), 3.79 (d, J = 11.1 Hz, 1H, H-1ꢀA), 3.54 (d, 1H, H-1ꢀB),
3.41–3.33 [m, 2H, H and 3.35 (dd, J2,3 = 9.7 Hz, 1H, H-2)], 3.05 (dd,
J5,6A = 3.1, J6A,6B = 13.2 Hz, 1H, H-6A), 2.77 (dd, J5,6B = 5.9 Hz, 1H, H-
6B), 1.28 (s, 9H, CMe3); 13C NMR (125 MHz): δ = 138.9, 138.54, 138.45,
138.35, 138.2, 138.0 (Cquart benzyl), 135.6, 135.5 (phenyl-C from TB-
DPS), 133.5, 133.2 (Cquart phenyl from TBDPS), 129.7, 129.6 (phenyl-C
from TBDPS), 104.7 (C-2ꢀ), 89.8 (C-1), 84.2, 82.8, 81.6, 81.5, 80.2, 79.8,
and 69.7 (C-2,3,3ꢀ,4,4,ꢀ,5,5ꢀ), 75.5, 74.7, 73.4, 73.1, 72.6, 72.0, 71.0 and
65.2 (CH2Ph, C-1ꢀ,6ꢀ), 42.8 (C-6), 27.0 (CMe3), 19.3 (CMe3). Anal. Calcd
for C140H150O20S2Si2: C, 73.98, H, 6.65; S, 2.82. Found: C, 74.0; H, 6.5;
S, 2.7%.
Bis-(6-deoxy-1ꢀ,2,3,3ꢀ,4,4ꢀ-hexa-O-benzylsucros-6ꢀ-yl)-disulfide
(16)
Protected disulfide 15 (0.144 g, 0.0635 mmol) was dissolved in THF
(10 mL), to which Bu4NF × 3 H2O (0.104 g, 0.33 mmol) was added. The
mixture was boiled under reflux for 2.5 h, and after cooling to room tem-
perature, was filtered through a short column with silica (hexane:ethyl
acetate, 3:2 as eluent). Evaporation of the solvent left crude product 16
in almost quantitative yield (0.122 g; this product according to NMR
was contaminated with small amounts of impurities). MS (ESI) m/z
= 1818.6 [(C108H114O20S2)+Na+], IR (νcm−1): 3475, 3031, 2916, 2868,
1
1454, 1362, 1088, 1070, 1026, 995, 737, 698. H NMR (500 MHz): δ =
5.59 (d, J1,2 = 3.5 Hz, 1H, H-1), 4.88 (d, JA,B = 11.0 Hz 1H), 4.84 (d,
JA,B = 10.9 Hz, 1H), 4.83 (d, JA,B = 11.0 Hz, 1H), 4.68 (d, JA,B = 10.9 Hz,
1H), 4.64–4.44 (m, 9 H), 4.39 (dd, J = 8.0, J = 8.0 Hz, 1H), 4.29 (d,
JA,B = 12.0 Hz, 1H), 4.22 (ddd, J = 3.5, J = 3.5, J = 9.8 Hz, 1H, H-5
or H-5 eluent:), 3.99–3.93 (m, 2H), 3.82 (dd, J = 2.3, J = 12.7 Hz, 1H),
3.67–3.60 (m, 1H), 3.59 (d, JA,B = 11.0 Hz, 1H, H-1ꢀA), 3.47 (d, 1H,
H-1ꢀB), 3.45 (dd, J2,3 = 9.8 Hz, 1H, H-2), 3.28 (dd, J5,6A = 3.5, J6A,6B
=
13.3 Hz, 1H, H-6A), 3.00 (dd, J5,6B = 3.6 Hz, 1H, H-6B), 13C NMR (125
MHz,): δ = 138.7, 138.3, 138.24, 138.21, 138.1, 137.9 (Cquart benzyl),
103.9 (C-2 eluent:), 90.5 (C-1), 83.6, 81.6, 81.1, 79.8, 79.7, 78.7, and
70.2 (C-2,3,3ꢀ,4,4,ꢀ,5,5ꢀ), 75.4, 75.0, 73.3, 73.1, 73.0, 72.7, 71.4 and 61.4
(CH2Ph, C-1ꢀ,6ꢀ), 43.2 (C-6).

Sucrose Analogs Containing Sulfur Functionalities
1295
REFERENCES
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[8] A. J. Mancuso, S.-L. Huang, and D. Swern, J. Org. Chem.,43, 2480 (1978).