Applications of Cyclic Sulfates of vic-Diols: Synthesis of Episulfides, Olefins, and Thio Sugars

Article abstract of DOI:10.1021/jo962066b

A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of inc-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate followed by treatment with sodium methoxide led to ep

Full text of DOI:10.1021/jo962066b

3944
J . Org. Chem. 1997, 62, 3944-3961
Ap p lica tion s of Cyclic Su lfa tes of vic-Diols: Syn th esis of
Ep isu lfid es, Olefin s, a n d Th io Su ga r s
Francisco G. Calvo-Flores, Pilar Garc´ıa-Mendoza, Fernando Herna´ndez-Mateo,
J oaqu´ın Isac-Garc´ıa, and Francisco Santoyo-Gonza´lez*
Instituto de Biotecnologı´a, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain
Received November 4, 1996X
A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of
vic-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate
followed by treatment with sodium methoxide led to episulfides. Olefins were obtained when
potassium selenocyanate was used as nucleophile, and the obtained monoesters were treated with
sodium borohydride. This method was applied to acyclic polyols derived from chiral glycerine, 1,2-
isopropylidenehexofuranoses with different subtituents at C-3, and dimethyl acetals derived from
pentoses and hexoses. The methodology is highly versatile, and its applicability has been
demonstrated by the synthesis of different 4- and 5-thiosugars by opening of the thiirane ring with
sodium acetate or lithium aluminum hydride. Reduction with lithium aluminum hydride of the
thiocyanate sulfate potassium salt obtained by the opening of cyclic sulfate with KSCN allowed
the direct synthesis of 5-deoxy-4-thio- and 6-deoxy-5-thiosugars. Cyclic thiosugars with the sulfur
atom in the ring are obtained by acidic hydrolysis of the 5-thiol derivatives of 1,2-O-isopropylidene-
hexofuranoses and 4-thiopentose dimethyl acetals. Using this method, an efficient synthesis of
5-thio-L-fucose as well as the synthesis of 2,5-dideoxy-4-thiofuranose is described.
In tr od u ction
titanium metals,19,20 Me3SiCl-NaI,21 Ph3P-imidazole-
I2,22 and PBr3-CuBr-ether followed by zinc powder.23
vic-Diols can also be deoxygenated indirectly by their
previous conversion into sulfonate ester derivatives,24-28
bisdithiocarbonates,29 cyclic thionocarbonates,30-43
oxiranes,44-49 episulfides,14,50-54 cyclic orthoformiates,32,55
vic-Diols have been widely used as precursors for the
synthesis of episulfides and olefins, which are very
versatile functions in organic synthesis. The synthesis
of episulfides1 generally involves the previous transfor-
mation of the diol into the corresponding epoxide and
opening with thiocyanate ions or with thiourea,2-12 which
are the most common reagents used for this transforma-
tion. A recently described method for the synthesis of
thiiranes involves a previous transformation of allylic
alcohols into cyclic xanthates.13-15 Olefins can be ob-
tained from vic-diols by a variety of different methods.16,17
For example, direct conversion of vic-diols into alkenes
is possible by treatment with tungsten reagents,18
(18) Sharpless, K. B.; Flood, T. C. J . Chem. Soc., Chem. Commun.
1972, 370.
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* To whom correspondence should be addressed. Tel.: +34-58-
243187. Fax: +34-58-243320. E-mail: fsantoyo@goliat.ugr.es.
X Abstract published in Advance ACS Abstracts, May 15, 1997.
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S0022-3263(96)02066-X CCC: $14.00 © 1997 American Chemical Society

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3945
and cyclic phosphates, phosphoroamidates,56-58 and sul-
fates.59,60
In spite of the variety of available methods for the
synthesis of episulfides and olefins from vic-diols, men-
tioned above, the use of the cyclic sulfates for the
preparation of these functions has not been explored in
depth. Cyclic sulfites and cyclic sulfates have been
known for a long time, and the use of these compounds
has been recently reviewed.61-63 Nucleophilic reactions
using cyclic sulfates as substrates are perhaps the most
commonly studied reactions, and the high reactivity of
these compounds as nucleophile acceptors is well known.
Analogous to epoxides, cyclic sulfates can be opened by
attack of a variety of nucleophiles at either carbon center.
However, unlike oxiranes, the cyclic sulfate opening
involves the generation of a sulfate monoester, allowing
further transformations. The generated sulfate is itself
a leaving group and can be subsequently displaced by a
nucleophile, giving rise to an overall substitution of both
2-
OH groups. Since a SO4 dianion is a much worse
leaving group than a ROSO3- anion, the second displace-
ment would be effected by the nucleophile incorporated
to the molecule in an intramolecular fashion. These
double displacement scenarios suggest a variety of useful
transformations than can make the chemistry of cyclic
sulfates more versatile than that of epoxides. To the best
of our knowledge, this methodology has only been applied
to the synthesis of cyclopropanes by reaction of cyclic
sulfates with malonate anion64 and methyl benzyl-
ideneglicinate.65-67 Taking into account all of these facts
and considerations, we have explored the use of cyclic
sulfates as precursors of episulfides and olefins. Pre-
liminary studies have shown68 that the treatment of cyclic
sulfates with potassium thioacetate followed by reaction
F igu r e 1.
with sodium methoxide allowed the one-pot transforma-
tion into episulfides. Similarly, reaction with potassium
selenocyanate followed by treatment with sodium boro-
hydride led to olefins also in one pot (see Figure 1).
Simultaneously to our studies, cyclic sulfates of vic-diols
have also been transformed into olefins by treatment with
phosphine69 or by telluride ion generated in situ by
reduction of elemental Te.70
On the other hand, in both chemical and biochemical
conversion of carbohydrates, cleavage and formation of
carbon-oxygen bonds at the anomeric center are the
most important reactions wherein the ring oxygen in the
furanose or pyranose structure plays a decisive role. It
is for this reason that thio sugars (sulfur in the ring of
the sugar) as sugar analogs have attracted attention.71
Most syntheses of thio sugars such as 4-thiofuranoses
and 5-thiopyranoses are based on the introduction of a
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thiol group at the 4- or 5-position, respectively.
A
classical approach for this functionalization, involving
episulfide opening by nucleophiles, has been used to
synthesize 5-thio-D-glucopyranose,72-75 5-thio-D-man-
nopyranose,76 5-thio-D-galactopyranose,77 2-acetamido-
2-deoxy-5-thio-D-glucopyranose
(5-thio-N-acetyl-D-
glucosamine),78-80 2-acetamido-2-deoxy-5-thio-R-D-man-
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3946 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
nopyranose,81 5-thio-L-idopyranose,82,83 5-thio-L-fucose,84
D- and L-2-deoxy-4-thioriboses,15 and 4-thiofuranoses.85
Nucleophilic replacement of a sulfonyloxy group by an
RS- group has been the common way for the introduction
of sulfur into sugar molecules such as 5-thio-D-xylopy-
ranose,83,86,87 5-thio-D-ribopyranose,74 5-thio-L-rhamnose,88
5-thio-L-fucose,89 4-thio-D-ribofuranose,90,91 and 5-thio-D-
arabinopyranose.89 In addition to such classical ap-
proaches, new routes to sulfur ring thio sugars based on
intramolecular cyclization of dithioacetals,92-96 conversion
of pyranosides into 5-thiopyranoside via monothioac-
etals,97,98 modification of optically pure Diels-Alder
aducts,99 and enzymatic synthesis100,101 have also been
reported.
not separated and were directly used in the oxidation
reaction with NaIO4-RuCl3‚3H2O. All of these sulfates
are stable compounds at low temperature (-5 °C) for
periods of 2 months. In addition to these cyclic sulfates,
the commercial cyclic sulfate 19 derived from 1,2:5,6-di-
O-isopropylidene-D-mannitol was also used (Schemes 1
and 2).
The synthesis of episulfides was carried out by nucleo-
philic ring opening of the cyclic sulfates with potassium
thioacetate and potassium thiocyanate. As expected, in
terminal cyclic sulfates of type II the nucleophilic attack
happened in a regiospecific fashion to the less hindered
primary position leading to â-acetylthio or â-thiocyanate
sulfates type III (Figure 1). We performed the reactions
of cyclic sulfates 3, 9a ,c-f, 15a ,b with potassium thio-
acetate or potassium thiocyanate in dry acetone at room
temperature, and the corresponding salts (4, 5, 10a ,c-
f, 11a ,c-f, 16a ,b, 17a ) were easily isolated in high yields
(72-100%) as stable solids that can be stored under
vacuum for several months (Scheme 1). These salts were
purified in order to carry out the complete characteriza-
tion of these compounds, but for preparative purposes
they were directly used without purification. Treatment
of these potassium salts with NaOMe-MeOH generated
the corresponding sodium thiolates that produced the
intramolecular displacement of the â-sulfate groups,
affording the corresponding episulfides (6, 12b-f, 18a ,b)
in good to high yields (63-95%). The nucleophilic
displacement occurred via an inversion of the configu-
ration at the â-chiral atom (Scheme 1).
The opening of the nonterminal cyclic sulfate 19 could
not be accomplished with potassium thioacetate even
when the experimental conditions (temperature and
solvent) were changed. However, when sodium sulfide
was used as nucleophile in boiling methanol, the desired
episulfide 20 was directly obtained in 42% yield (Scheme
2). Considering this result, we attempted the direct
synthesis of episulfides from terminal cyclic sulfates
using sodium sulfide, but reaction of compounds 9a ,d
with this reagent led to the sulfides 21 and 22, respec-
tively, in good yields (Scheme 2). The different behavior
of compounds 19 and 9a ,d showed that when the cyclic
sulfate was sterically hindered, as in the nonterminal
cyclic sulfate 19, the intramolecular attack was favored.
Nonetheless, in the less hindered terminal cyclic sulfate,
such as 9a ,d , the intermolecular displacement was
favored and the corresponding dimeric sulfides are
exclusively obtained. As a result, in our laboratory we
are investigating the exploitation of this method for the
synthesis of sulfides.
In this paper, we expand upon our preliminary re-
sults68 and report on the versatility of cyclic sulfates as
precursors of olefins, episulfides and thiols as well their
uses in the synthesis of thio sugars (thiofuranoses and
thiopyranoses) (see Figure 1).
Resu lts a n d Discu ssion
The following vic-diols were selected for this study:
Acyclic polyols derived from chiral glycerine (1) and
D-mannitol (35) were chosen for their structural simplic-
ity; 1,2-O-isopropylidenehexofuranoses with different
subtituents at C-3 (7a ,c-f) were chosen in order to carry
out the synthesis of 5-thio sugars; and dimethyl acetals
derived from pentoses (13b) and hexoses (13a ) were
chosen in order to carry out the synthesis of 5-thiopyra-
noses and 4-thiofuranoses. The cyclic sulfates (3, 9a ,c-
f, 15a ,b, 36) of these diols were easily obtained in high
yields via the corresponding cyclic sulfites following the
general procedure described by Gao and Sharpless.64 In
general, the diasteromeric mixtures of cyclic sulfites were
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The method described above constitutes a short, easy,
and efficient method for the synthesis of episulfides from
vic-diols. Access to episulfides can be had by using either
the potassium thioacetate or thiocyanate salts, but yields
are slightly higher when the former salt is employed. It
should also be mentioned that similar compounds to 6,
namely, (2R)- and (2S)-1-O-(tert-butyldiphenylsilyl)-2,3-
epithiopropanol, have recently been synthesized starting
from (R)- and (S)-glycidol by reaction with thiourea and
employed in a high-yielding synthesis of 2′,3′-dideoxy-
and 2′,3′-didehydro-2′,3′-dideoxy-4′-thionucleosides, which
showed a marked anti-HBV and anti-HIV activity.102
When we observed the good results obtained on the
synthesis of episulfides, we considered the use of this
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Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3947
Sch em e 1a
a
Key: (i) SOCl2, Et3N, CH2Cl2; (ii) RuCl3‚3H2O, NaIO4, MeCN, CCl4, H2O; (iii) KSAc or KSCN, acetone; (iv) NaOMe, MeOH.
Sch em e 2a
Given the synthesis of episulfides, one would expect
that seliranes could be obtained by treatment of cyclic
sulfates with potassium selenocyanate. However, it is
known that seliranes are unstable and easily expel the
selenium atom giving alkenes;103 thus, cyclic sulfates
could be converted to olefins in one pot. This hypothesis
was confirmed when we performed the reaction of 9a ,c-f
and 15a with potassium selenocyanate (Scheme 4). The
corresponding seleno derivatives 31a ,c-f and 33 were
isolated as solids in high yields. These compounds,
unlike the thioacetate and thiocyanate salts, are unstable
and slowly decomposed at rt. We isolated these salts for
their characterization, but for preparative purposes they
were used without purification in the next step. Reaction
of the furanose selenocyanate salts 31a ,c-f with sodium
borohydride in methanol at room temperature gave the
olefins 32b-f in 50-94% yields. Similar treatment of
the acyclic dimethyl acetal 33 led to the olefin 34 in 59%
yield. These compounds could be used as precursors of
5-hexenals, which have been employed in radical cycliza-
tion reactions for the synthesis of cyclopentanols.104,105
As in 34, the diolefin 37 was synthesized in moderate
yield (45%) from the cyclic disulfate 36 by reaction of 36
with potassium selenocyanate followed by treatment with
sodium borohydride.
a
Key: (i) Na2S‚9H2O, methanol, reflux; (ii) Na2S‚9H2O, acetone-
H2O, rt.
methodology for the preparation of thietanes from 1,3-
diols. With this objective in mind, we performed the
synthesis of the cyclic sulfates 24 and 28 (Scheme 3).
Both compounds were stable crystalline solids that were
obtained from diols 23 and 27, as described above, in 48%
and 58% overall yields, respectively. Nucleophilic ring
opening of the cyclic sulfate with potassium thioacetate
gave the γ-acetylthio sulfates 25 (86% yield) and 29 (94%
yield). However, neither of these two compounds could
be transformed into the desired thietanes 26 and 30 when
treated with NaOMe-MeOH (Scheme 3). In this case,
the formation of highly polar compounds was observed,
but the compounds were not further investigated.
Given that by following the methodology described
above L-sugar episulfides are obtained from D-sugars, we
could apply such methodology as an expeditious and
(103) van Ende, D.; Krief, A. Tetrahedron Lett. 1975, 31, 2709.
(104) Grove, J . J . C.; Holzapfel, C. W.; Williams, B. G. Tetrahedron
Lett. 1996, 37, 5817.
(105) Grove, J . J . C.; Holzapfel, C. W.; Williams, D. B. G. Tetrahe-
dron Lett. 1996, 37, 1305.

3948 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
Sch em e 3a
(37%) together with the elimination product allyl benzyl
ether. Similar reaction with the episulfide furanose
derivatives 12a ,c,d gave exclusively the 5-thio-L-idofura-
noses derivatives 39a ,c,d in good yields (61-95%). When
the starting material was the thiirane derived from
L-idosamine 18a , the corresponding 5-thio sugar 42a was
isolated as the major product (60% yield) together with
the olefin 34 as the minor compound (15%) (Scheme 5).
It should be noted that formation of olefins from episul-
fides is not an unusual process, as thiirane thermal
desulfurization has previously been described.106-112
6-Deoxy-5-thio-L-sugars 40b,d and 43a and 5-deoxy-4-
thio-L-sugars 43b were obtained by reduction of the
corresponding episulfides 12b,d , 18a , and 18b, respec-
tively (Scheme 5). Lithium aluminum hydride was
employed as the reducing reagent, and the reactions were
performed at room temperature using a 4-fold molar
excess of this reagent relative to the thiirane, thus
allowing the isolation of the thiol derivatives in good to
high yields (66-98%). These results are in sharp con-
trast with those that were recently described by Kusz-
mann et al.113 on the synthesis of 6-deoxy-5-thio-D-glucose
using 5,6-dideoxy-5,6-epithio-1,2-O-isopropylidene-R-D-
glucofuranose and its 3-O-allyl derivative as starting
materials. Under similar reaction conditions, these
authors reported the isolation of 6-deoxy-1,2-O-isopro-
pylidene-5-thio-R-D-glucofuranose in low yields along
with the formation of di- and trimers.
In spite of the satisfactory results obtained in the
synthesis of L-thio sugars by means of the sequence of
reactions described above (formation of cyclic sulfate-
ring opening with potassium thiocyanate or thioacetate-
formation of the episulfide-reduction), we thought that
the number of steps could be reduced if the potassium
thiocyanate salts of type III (Nu ) SCN) (Figure 1)
reacted directly with lithium aluminum hydride. We
anticipated that the reduction of the thiocyanate function
would afford the Li-thiolate salt and that this compound
would undergo the intramolecular nucleophilic displace-
ment of the â-sulfate group, yielding the corresponding
episulfide. In addition, under the reducing conditions,
the episulfide formed would be reduced and the thiol
derivative of type IV would be obtained. As expected,
treatment of 11a ,c,d and 17a with LiAlH4 (6 equiv) at
rt afforded the thiol derivatives 40b,c,d and 43a , respec-
tively, with yields in the range of 31-84%. Conventional
acetylation of 40b,c,d gave the corresponding acetylated
derivatives 41a ,c,d , respectively (Scheme 5). When the
reduction was performed on the thiocyanate potassium
salt 11f, simultaneous reduction of the azido group
happened and the 3-amino-3,6-dideoxy-5-thio sugar 41g
was isolated as its N,S-diacetyl derivative after standard
acetylation of the crude product (Scheme 5). This route
may allow a short synthesis of 3-amino-3,6-dideoxy-5-
thio- and 3-amino-2,3,6-trideoxy-5-thio-L-sugars, which
are analogs to the important antibiotic components
a
Key: (i) (a) SOCl2, Et3N, CH2Cl2; (b) RuCl3‚3H2O, NaIO4,
MeCN, CCl4, H2O; (ii) KSAc, acetone; (iii) NaOMe, MeOH.
Sch em e 4a
(106) Parhan, W. E.; Koncos, R. J . Am. Chem. Soc. 1961, 83, 4034.
(107) Vollhardt, K. C. P.; Bergman, R. G. J . Am. Chem. Soc. 1973,
95, 7538.
(108) Ando, W.; Itami, A.; Furuhata, T.; Tokitoh, N. Tetrahedron
Lett. 1987, 28, 1787.
(109) Lutz, E.; Biellmann, J . F. Tetrahedron Lett. 1985, 26, 2789.
(110) Bouda, H.; Borredon, M. E.; Delmas, M.; Gaset, A. Synth.
Commun. 1989, 19, 491.
(111) Williams, C. R.; Harpp, D. N. Sulfur Rep. 1990, 10, 103.
(112) Chew, W.; Harpp, D. N. MTP Int. Rev. Sci. Org. Chem., Ser.
Two 1992, 1.
a
Key: (i) KSeCN, acetone, rt; (ii) NaBH4, MeOH; (iii) (a) SOCl2,
Et3N, CH2Cl2; (b) RuCl3‚3H2O, NaIO4, MeCN, CCl4, H2O.
inexpensive strategy for the synthesis of L-thio sugars.
The nucleophilic ring opening of the episulfide 6 with
sodium acetate in acetic acid-acetic anhydride at 120
°C under an argon atmosphere allowed the isolation of
the acetylated thiol derivatives 38 in moderate yield
(113) Bozo´, E.; Boros, S.; Kuszmann, J . Carbohydr. Res. 1996, 290,
159.

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3949
Sch em e 5a
a
Key: (i) Ac2O, AcOH, NaOAc; (ii) LiAlH4, THF; (iii) Ac2O-Py.
Sch em e 6a
3-amino-2,3,6-trideoxy-L-hexoses.114 Implementation of
this strategy with this purpose is currently under re-
search in our laboratory.
The next step, the incorporation of the sulfur atom into
the carbohydrate ring in order to obtain the thio sugars
as thiohexopyranoses and thiopentofuranoses, was car-
ried out by acid treatment of the thiol derivatives
obtained in the thiirane opening by the nucleophilic
acetate or hydride. We performed this transformation
using only compounds 39a ,c,d , 41a ,c,d , and 43b. Hy-
drolysis of the 1,2-O-isopropylidene group in 39a ,c,d and
41a ,c,d using aqueous acetic acid was followed by treat-
ment with catalytic amounts of NaOMe-MeOH (Zem-
ple´n deacetylation). The 5-thio-L-idopyranoses 44, 46, 48,
50, 52, and 54 were obtained as an R,â mixture of
anomers in 35-90% yields. We transformed these com-
pounds into the corresponding peracetylated derivatives
45, 47 49, 51, 53, and 55, respectively, by standard
acetylation. Compound 43b was also submitted to hy-
drolysis with aqueous acetic acid, and the 5-deoxy-4-thio-
R,â-L-arabinofuranose 56 was obtained in 54% yield
(Scheme 6).
It should be noted that the spectroscopic 1H NMR data
for the 5-thio-L-idopyranose hydroxyl derivatives 44, 46,
48, 50, 52, and 54 indicate that the preferred conforma-
4
tion for both R and â anomers is the C1, as deduced from
3
the J 1,2 coupling constant values that are in the range
7.1-8.3 Hz for the R-anomer and 2.5-3.4 Hz for the
â-anomer. The same is observed for the â-anomer in the
per-O-acetyl derivatives 45, 47 49, 51, 53, and 55, which
(114) Sztaricskai, F.; Pelyva´s, I. F. In Glycopeptide Antibiotics;
Nagarajan, R., Ed.; Marcel Dekker, Inc.: New York, 1994; pp 105-
193.
a
Key: (i) AcOH-H2O; (ii) NaOMe, MeOH; (iii) Ac2O-Py.

3950 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
3
Sch em e 7a
showed J 1,2 values of 3.4-3.6 Hz. However, the R-ano-
mer of these compounds suffers a puckering of the ring
as deduced from the decrease of the J 1,2 coupling
3
constant (5.5-7.2 Hz). These data are in agreement with
the prediction reported by Lambert et al.115 for 5-thio-D-
glucose. Unambiguous assignment of the 13C NMR
signals was possible by 2D correlation experiments in
compounds 44, 47-51, and 53-55. In all cases, the
resonances of C-1 are in the range 71.4-75.5 ppm, in
accordance with the data reported by Lambert et al.115
for 5-thio-D-glucose. However, a slight shielding of the
R-anomer carbon-1 with respect to the â-anomer carbon-1
is observed in each pair of anomers. This is in contrast
to the generally observed fact116 that the chemical shift
of the signals of an anomeric carbon bearing an equato-
rial substituent is at lower field (∼5 ppm) than that with
an axial one. This behavior is also observed in the
thiofuranoses 56 where the differences of the resonances
are even smaller (78.5 ppm for C-1b and 78.0 ppm for
C-1a).
a
Key: (i) AcOH, H2O; (ii) SOCl2, Et3N, CH2Cl2; (iii) RuCl3‚3H2O,
NaIO4, MeCN, CCl4, H2O; (iv) KSCN, acetone; (v) LiAlH4, THF.
Once the efficiency of the method described above for
the synthesis of L-thio sugars was demonstrated, the
strategy was applied in the synthesis of 5-thio-L-fucose
and 2-deoxy-4-thiofuranoses, both important because of
their biological significance. Hashimoto et al.84 were the
first authors to report the synthesis 5-thio-R-L-fucose
and its specific and potent inhibitory activity against
bovine R-L-fucosidases with Ki values in the millimolar
range. These authors have later described other methods
for the synthesis of 5-thio-R-L-fucose89 and some fucopy-
ranoside derivatives117 as well as several 5-thio-R-L-
fucopyranosyl disaccharides118 and analogues of the blood
group antigen H-type 2 and of Lewis X (Lex).119 We
envisaged the synthesis of 5-thio-L-fucose using 1,2:5,6-
di-O-isopropylidene-â-D-altrofuranose120,121 57 as starting
material and following the sequence of reactions indi-
cated in Scheme 7. All the reactions were high yielding
(>83%), and an R,â anomeric mixture of 5-thio-L-fucose
(63) was obtained in 57.0% overall yield from 57. As
expected, the R-anomer was the major component and
the â-anomer was only detected in the mother liquors of
crystallization. When compared with the method de-
scribed by Hashimoto et al.,84 which also employed 57
as the starting material, the use of the cyclic sulfate
strategy allowed a considerable increase in the overall
yield of the synthesis (57.0% vs 18.0%).
Sch em e 8a
On the other hand, the synthesis of nucleosides in
which the sugar moiety is modified by the replacement
of furanose ring oxygen atom with a sulfur atom has
attracted attention because an increase in the metabolic
stability of these compounds toward phosphorylase en-
zymes is known to occur.122 Consequently, 2′-deoxy-4′-
thionucleosides could be especially advantageous to an
antiviral strategy when incorporated into a DNA ma-
a
Key: (i) (a) Me2C(OMe)2, acetone, P2O5; (b) KtBuO, DMSO,
THF; (c) LiAlH4, THF; (d) BnBr, NaH, THF; (e) AcOH, H2O; Ac2O-
Py; (ii) (a) NBS, MeOH; (b) NaOMe, MeOH; (iii) SOCl2, Et3N,
CH2Cl2; (iv) RuCl3‚3H2O, NaIO4, MeCN, CCl4, H2O; (v) KSAc,
acetone, 77%; (vi) NaOMe, MeOH; (vii) Ac2O, AcOH, NaOAc; (viii)
LiAlH4, THF, 36%; (ix) Ac2O-Py; (x) AcOH, H2O; NaOMe, MeOH;
70%.
trix.123 Several routes for the synthesis of these thio
sugars, with a special emphasis in the preparation of
2-deoxy-4-thioribose, have been published96 using carbo-
hydrate and nonsaccharide compounds as starting ma-
terials. Use of cyclic sulfates allows a new route for the
synthesis of 2-deoxy-4-thiofuranosides as depicted in
Scheme 8. 3-O-Benzyl-2-deoxyaldehydo-L-erythro-pen-
tose dimethyl acetal (66) was chosen as the starting
hydroxylated derivative as this compound is easily
prepared from L-arabinose diethyl dithioacetal124 accord-
(115) Lambert, J . B.; Wharry, S. M. J . Org. Chem. 1981, 46, 3193.
(116) Perlin, A. S. MTP Int. Rev. Sci. Org. Chem., Ser. Two 1976,
1.
(117) Tsuruta, O.; Yuasa, H.; Hashimoto, H. Bioorg. Med. Chem.
Lett. 1996, 6, 1989.
(118) Hashimoto, H.; Izumi, M. Tetrahedron Lett. 1993, 34, 4949.
(119) Izumi, M.; Tsuruta, O.; Hashimoto, H.; Yazawa, S. Tetrahe-
dron Lett. 1996, 37, 1809.
(120) Fujita, K.; Ohta, K.; Ikegami, Y.; Shimada, H.; Tahara, T.;
Nogami, Y.; Koga, T.; Saito, K.; Nakajima, T. Tetrahedron Lett. 1994,
35, 9577.
(121) Fuller, T. S.; Stick, R. V. Aust. J . Chem. 1980, 33, 2509.
(122) Parks, R. E.; Stoeckler, J . D.; Cambor, C.; Savarese, T. M.;
Crabtree, G. W.; Chu, S.-H. In Molecular Actions and Targets for
Cancer Chemotherapeutic Agents; Sartorelli, A. C., Lazo, J . S., Bertino,
J . S., Eds.; Academic Press: New York, 1981.
(123) Secrist, J . A., III; Tiwari, K. N.; Riordan, J . M.; Montgomery,
J . A. J . Med. Chem. 1991, 34, 2361.

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3951
ing to the procedure developed by Wong and Gray.125
Cyclic sulfate 68 was obtained in high yield (95.0%)
following the general procedure described in this paper,
but, unlike other cyclic sulfates, it decomposed not only
during its column chromatographic purification but also
when the crude product was left at rt for several hours.
Therefore, compound 68 was used immediately after
workup and transformed into the episulfide 70 via the
potassium thioacetate salt 69 in 64.0% overall yield.
When episulfide 70 was heated in acetic acid and acetic
anhydride in the presence of sodium acetate methyl
2-deoxy-4-thiofuranoside 71 was isolated in low yield
(30%). This direct transformation of episulfides into
thiofuranoses occurred in accordance with previous ob-
servations described by Uenishi et al.15 for similar
2-deoxy acetals of pentoses but was not being observed
in acetal 18a , which has an acetamido group at the C-2
position. 2,5-Dideoxy-4-thiofuranose 74 was obtained
from episulfide 70 following the sequence of reactions
described for the synthesis of thiopyranoses in 24% yield.
Both 2-deoxythiosugars 71 and 74 were isolated as
inseparable mixtures of R,â-anomers.
dithioacetal (64) (90%) using the method described by Zinner
et al.124 The reaction of this compound with acetone according
with to the procedure described by van Es131 gave 2,3:4,5-di-
O-isopropylidene-L-arabinose diethyl dithioacetal (92%). Fol-
lowing the method of Wong and Gray,125 this protected
arabinose derivative was converted to 2-deoxy-4,5-O-isopro-
pylidene-L-erythro-pen-1-enose diethyl dithioacetal that was
isolated as a syrup (96% yield): [R]D -6° (c 6.5, chloroform);
IR (neat) 3411, 1683, 1580 cm-1; 1H NMR (CDCl3) δ 5.91 (d, 1
H, J ) 7.9 Hz), 4.89 (m, 1 H), 4.16 (dt, 1 H, J ) 6.7, 4.3 Hz),
3.97 (dd, 1 H, J ) 8.2, 6.6 Hz), 3.87 (dd, 1 H, J ) 8.3, 6.9 Hz),
2.92-2.65 (m, 4 H), 2.25 (d, 1 H, J ) 2.9 Hz), 1.43, 1.35 (2 s,
6 H), 1.25, 1.23 (2 t, 6 H, J ) 7.7 Hz); 13C NMR (CDCl3) δ
135.7, 133.0, 109.5, 78.0, 69.7, 65.1, 27.6, 27.2, 26.5, 25.3, 15.1,
14.0; MS m/z 261 (M+ + 1 - H2O). This compound was treated
with LiAlH4 to give 2-deoxy-4,5-O-isopropylidene-L-erythro-
pentose diethyl dithioacetal as a syrup (90% yield): [R]D +8°
(c 2, chloroform); IR (neat) 3450, 1258, 1215, 1156, 1065 cm-1
;
1H NMR (CDCl3) δ 4.09-3.91 (m, 5 H), 2.76-2.54 (m, 4 H),
2.00 (ddd, 1 H, J ) 14.6, 9.2, 2.5 Hz), 1.86 (ddd, 1 H, J ) 14.6,
9.4, 5.3 Hz), 1.42, 1.35 (2 s, 6 H), 1.27, 1.26 (2 t, 6 H, J ) 7.4
Hz); 13C NMR (CDCl3) δ 109.3, 78.4, 70.3, 65.6, 48.3, 38.9, 26.6,
26.2, 24.4, 23.9, 14.5, 14.4. Conventional benzylation of this
compound followed by hydrolysis with aqueous acetic acid
(70%) at 70 °C and standard acetylation with acetic anhydride-
pyridine gave after workup 4,5-di-O-acetyl-3-O-benzyl-2-deoxy-
L-erythro-pentose diethyl dithioacetal (65) as a syrup (78.2%
yield): [R]D -2° (c 4, chloroform); IR (neat) 1740 cm-1; 1H NMR
(CDCl3) δ 7.32 (m, 5 H), 5.29 (ddd, 1 H, J ) 7.2, 3.4, 3.4 Hz),
4.62 (AB system, 2 H, J ) 11.1 Hz, δν ) 29.6 Hz), 4.35 (dd, 1
H, J ) 12.1, 3.4 Hz), 4.14 (dd, 1 H, J ) 12.1, 7.3 Hz), 4.00
(ddd, 1 H, J ) 9.6, 3.3, 3.2 Hz), 3.94 (dd, 1 H, J ) 10.5, 4.3
Hz), 2.69-2.49 (m, 4 H), 2.14 (ddd, 1 H, J ) 14.5, 9.6, 4.3 Hz),
2.08, 2.94 (2 s, 6 H), 1.84 (ddd, 1 H, J ) 14.5, 10.5, 3.2 Hz),
1.22 (t, 6 H, J ) 7.5 Hz); 13C NMR (CDCl3) δ 170.5, 170.3,
138.0, 128.5, 128.1, 127.9, 76.2, 73.0, 72.4, 62.7, 47.7, 37.9, 24.5,
23.5, 21.1, 20.8, 14.5; MS m/z 354 (M+ + 1 - C2H4O2), 265,
247.
Con clu sion
The results described in this paper demonstrate that
vic-diols are easily transformed into thiiranes and olefins
via cyclic sulfates in an expeditious form: vic-diol f cyclic
sulfite f cyclic sulfate f acyclic sulfate potassium salt
f thiirane or olefin. Both routes require four reactions
but need only two steps as the purification of the cyclic
sulfite and the acyclic potassium salts is not necessary.
In addition, all the reactions occurred with good to high
yields. The methodology is highly versatile, and its
applicability has been demonstrated for the synthesis of
thio sugars not only by conventional opening of the
episulfide ring with sodium acetate but also by direct
hydride reduction of the thiocyanate sulfate potassium
salt. For example, among other thio sugars synthesized
using this methodology we efficiently synthesized 5-thio-
L-fucose.
Compound 65 was treated with NBS in anhydrous metha-
nol132 followed by Zemple´n de-O-acetylation affording 3-O-
benzyl-2-deoxy-L-erythro-aldehydo-pentose dimethyl acetal (66)
as a syrup in 83.0% yield: [R]D +22° (c 1, ethyl acetate); IR
1
(neat) 3407, 1073 cm-1; H NMR (CDCl3) δ 7.40-7.20 (m, 5
H), 4.60 (AB system, 2 H, J ) 11.5 Hz, δν ) 16.8 Hz), 4.57
(dd, 1 H, J ) 7.6, 4.0 Hz), 3.80-3.50 (m, 6 H), 3.26, 3.24 (2 s,
6 H), 1.94 (ddd, 1 H, J ) 14.4, 7.6, 3.4 Hz), 1.79 (ddd, 1 H, J
) 14.4, 8.8, 4.0 Hz); 13C NMR (CDCl3) δ 141.9, 130.8, 130.3,
129.9, 104.8, 79.8, 76.1, 74.6, 65.7, 54.6, 54.5, 36.8.
Exp er im en ta l Section 126
Gen er a l P r oced u r e for th e Syn th esis of Cyclic Su lfites
2, 8a ,c-f, 14a ,b, 59, a n d 67. An ice-cooled and magnetically
stirred solution of the diol 1, 7a ,c-f, 13a ,b, 58, and 66 (5
mmol) and Et3N (20 mmol) in dry CH2Cl2 (20 mL) was added
to a CH2Cl2 solution (15 mL) of SOCl2 (7.5 mmol) dropwise
over a period of 10 min. Stirring was continued at 0 °C, until
TLC (ether) showed complete disappearance of starting mate-
rial. The mixture was diluted with CH2Cl2 (50 mL) and
washed with water (2 × 50 mL) and brine (100 mL). The
organic solution was dried (Na2SO4) and filtered. The filtrate
Sta r tin g Ma ter ia ls. Compounds 1 and 19 were purchased
from Sigma and Fluka Co, respectively. Compounds 7a ,c,d
were prepared from 1,2:5,6-di-O-isopropylidene-R-D-glucofura-
nose in two steps by conventional acetylation or alkylation
(methylation or benzylation) followed by selective hydrolysis
of the 5,6-O-isopropylidene group. Compounds 7e,f were
obtained according to the procedures described by J ust et al.127
and by Baer et al.,128 respectively. Compounds 13a ,b were
obtained following the procedure described by Hasegawa et
al.129 Compound 57 was obtained from methyl R-D-altropy-
ranose120,130 following the method described by Fuller et al.121
3-O-Ben zyl-L-er yth r o-a ld eh yd o-p en tose Dim eth yl Ac-
eta l (66). L-Arabinose was converted to L-arabinose diethyl
was concentrated on
a rotary evaporator under reduced
pressure to give a mixture of the corresponding cyclic sulfites,
which were purified by a short column chromatography.
(2R)-1-O-Ben zylglycer ol 2,3-Cyclic Su lfite (2). Column
chromatography (ether-hexane 1:1) of the crude product gave
2 (mixture of stereoisomers) (98.5%) as a syrup: IR (neat)
1208, 1106 cm-1; 1H NMR (CDCl3) δ 7.30-7.25 (m, 5 H), 5.07
(m, ∼0.5 H), 4.69 (dd, ∼0.5 H, J ) 8.4, 6.6 Hz), 4.66 (m, ∼0.5
H), 4.60-4.52 (m, 3 H), 4.31 (dd, ∼0.5 H, J ) 8.4, 5.2 Hz),
3.87 (dd, ∼0.5 H, J ) 10.2, 5.3 Hz), 3.78 (dd, ∼0.5 H, J ) 10.2,
6.0 Hz), 3.62 (dd, ∼0.5 H, J ) 10.4, 4.8 Hz), 3.55 (dd, ∼0.5 H,
J ) 10.4, 5.5 Hz); 13C NMR (CDCl3) δ 137.3, 128.6, 128.1,-
127.9, 127.8, 81.1, 78.5, 73.8, 73.7, 70.2, 69.4, 68.8, 68.4; MS
m/z 229 (M+ + 1), 181, 91.
(124) Zinner, H. Chem. Ber. 1951, 84, 780.
(125) Wong, M. Y. H.; Gray, G. R. J . Am. Chem. Soc. 1978, 100,
3548.
(126) For typical experimental protocols see: Santoyo-Gonza´lez, F.;
Calvo-Flores, F. G.; Garc´ıa-Mendoza, P.; Herna´ndez-Mateo, F.; Isac-
Garc´ıa, J .; Robles-D´ıaz, R. J . Org. Chem. 1993, 58, 6122. 1H and 13C
spectra were recorded at 300 MHz and when specified at 400 or 500
MHz. 1H and 13C resonances for compounds 44, 47-51, 53-56, and
63 were assigned by 1H-1H COSY and 13C-1H correlation experi-
ments.
(127) J ust, G.; Luthe, G.; Oh, H. Tetrahedron Lett. 1980, 21, 1001.
(128) Baer, H. H.; Gan, Y. Carbohydr. Res. 1980, 210, 233.
(129) Hasegawa, A.; Kiso, M. Carbohydr. Res. 1980, 79, 265.
(130) Ritchmyer, N. K. Methods Carbohydr. Chem. 1962, I, 107.
(131) van Es, T. Carbohydr. Res. 1974, 32, 370.
(132) Miljkovic, D.; Popsavin, M.; Popsavin, V.; Vukojevic, N.;
Harangi, J .; Ma´k, M. Carbohydr. Res. 1989, 194, 300.

3952 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
3-O-Acetyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8a ). Column chromatography (ether) of the
crude product gave 8a (82%). The mixture of the two stere-
oisomers could be resolved by column chromatography (ether-
hexane, 1:1) using an analytical sample. The first stereoiso-
mer was a solid that showed the following physical data: mp
120-121 °C; [R]D +62° (c 1, chloroform); IR (KBr) 1731, 1384,
Hz), 4.96 (ddd, 0.5 H, J ) 6.4, 4.5 Hz), 4.81-4.60 (m, 3 H),
4.49 (dd, 0.5 H, J ) 4.6, 8.9 Hz), 4.26 (dd, 0.5 H, J ) 9.1, 4.6
Hz), 4.03 (dd, 0.5 H, J ) 9.2, 6.2 Hz), 3.70 (dd, 0.5 H, J ) 9.1,
4.8 Hz), 3.45 (dd, 0.5 H, J ) 9.2, 4.7 Hz), 1.57, 1.56, 1.36, 1.35
(4s, 6 H); 13C NMR (CDCl3) δ 113.8, 113.7, 104.2, 81.7, 80.5,
80.4, 79.3, 77.3, 76.6, 68.9, 68.5, 62.9, 62.5, 26.6, 26.5, 26.4,
26.4; MS m/z 292 (M+ + 1).
2-Aceta m id o-2-d eoxy-3,4-O-isop r op ylid en e-a ld eh yd o-
D-glu cose Dim eth yl Aceta l 5,6-Cyclic Su lfite (14a ). Col-
umn chromatography (ethyl acetate) of the crude product gave
14a (95%) as a syrup: IR (neat) 3298, 1662, 1541, 1455, 1373,
1213, 1124, 1089 cm-1; 1H NMR (CDCl3) δ 5.86 (d, 0.5 H, J )
8.7 Hz), 5.80 (d, 0.5 H, J ) 8.5 Hz), 4.87 (ddd, 0.5 H, J ) 7.3,
6.4, 4.1 Hz), 4.72 (dd, 0.5 H, J ) 8.8, 6.4 Hz), 4.69 (t, 0.5 H, J
) 9.2 Hz), 4.63 (dd, 0.5 H, J ) 9.1, 6.6 Hz), 4.52 (dd, 0.5 H, J
) 8.9, 4.2 Hz), 4.51 (dt, 0.5 H, J ) 9.1, 6.6 Hz), 4.45-4.25 (m,
2.5 H), 4.18 (dd, 0.5 H, J ) 8.0, 1.1 Hz), 4.02 (t, 0.5 H, J ) 7.1
Hz), 3.62 (t, 0.5 H, J ) 7.7 Hz), 3.37, 3.37, 3.33, 3.29 (4s, 6 H),
1.99, 1.99 (2s, 3H), 1.37, 1.34 (2s, 6 H); 13C NMR (CDCl3) δ
170.1, 169.9, 110.3, 110.2, 103.2, 102.9, 82.3, 80.4, 77.5, 77.5,
77.3, 75.9, 69.2, 55.5, 55.1, 53.8, 52.9, 49.5, 49.2, 27.0, 27.0,
26.9, 23.3; MS m/z 354 (M+ + 1), 322; MS (calcd mass for
C13H23NO8S + H 354.1222) obsd m/z 354.1225.
1
1265, 1242, 1185 cm-1; H NMR (CDCl3) δ 6.01 (d, 1 H, J )
3.8 Hz), 5.00 (d, 1 H, J ) 2.3 Hz), 4.71 (d, 1 H, J ) 3.8 Hz),
4.56 (dd, 1 H, J ) 13.3, 7.7 Hz), 4.44-4.36 (m, 3 H), 2.10 (s, 3
H), 1.51, 1.35 (2s, 6 H); 13C NMR (CDCl3) δ 169.7, 113.1, 105.2,
83.4, 74.1, 73.2, 69.2, 63.7, 26.8, 26.4, 20.8; MS m/z 309 (M+
+
1), 293, 251, 245, 187. Anal. Calcd for C11H16O8S: C, 42.85;
H, 5.23; S, 10.40. Found: C, 42.81; H, 5.26; S, 10.08. The
second stereoisomer eluted was a solid that showed the
following physical data: mp 110-111 °C; [R]D -67° (c 1,
1
chloroform); IR (KBr) 1749, 1376, 1265, 1209, 1166 cm-1; H
NMR (CDCl3) δ 5.89 (d, 1 H, J ) 3.6 Hz), 5.29 (d, 1 H, J ) 3.2
Hz), 5.03 (ddd, 1 H, J ) 8.0, 6.4, 4.1 Hz), 4.77 (dd, 1 H, J )
8.9, 6.4 Hz), 4.61 (dd, 1 H. J ) 8.9, 4.1 Hz), 4.52 (d, 1 H, J )
3.6 Hz), 4.22 (dd, 1 H, J ) 8.0, 3.2 Hz), 2.12 (s, 3 H), 1.50,
1.30 (2s, 6 H); 13C NMR (CDCl3) δ 169.2, 112.9, 105.3, 83.4,
77.8, 76.2, 75.5, 69.1, 26.8, 26.2, 20.9; MS m/z 309 (M+ + 1),
293, 251, 245,187. Anal. Calcd for C11H16O8S: C, 42.85; H,
5.23; S, 10.40. Found: C, 42.61; H, 5.36; S, 10.00.
2,3-O-Isop r op ylid en e-a ld eh yd o-D-xylose Dim eth yl Ac-
eta l 4,5-Cyclic Su lfite (14b). Column chromatography (ethyl
acetate) of the crude product gave 14b (81%) as a syrup: IR
1,2-O-Isopr opyliden e-3-O-m eth yl-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8c). Column chromatography (ether-hexane
1:1) of the crude product gave 8c (mixture of stereoisomers)
(neat) 1027, 999 cm-1
;
1H NMR (CDCl3) (selected signals) δ
5.06 (ddd, ∼0.5 H, J ) 6.9, 5.0, 2.5 Hz), 4.72 (dd, ∼0.5 H, J )
8.3, 6.9 Hz), 4.42 (d, 0.5 H, J ) 5.5 Hz), 3.47, 3.46, 3.45, 3.44
(4 s, 6 H), 1.46, 1.44, 1.43, 1.40 (4 s, 6 H);
1
(85%) as a syrup: IR (neat) 1295, 1213, 1165, 1124 cm-1; H
NMR (CDCl3) δ 5.87 (d, 1 H, J ) 3.5 Hz), 5.12 (dt, 0.5 H, J )
6.6, 4.8 Hz), 4.73-4.56 (m, 3 H), 4.52 (dd, 0.5 H, J ) 8.8, 4.8
Hz), 4.43 (dd, 0.5 H, J ) 8.0, 3.2 Hz), 4.21 (dd, 0.5 H, J ) 6.6,
3.3 Hz), 3.86 (d, 0.5 H, J ) 3.2 Hz), 3.79 (d, 0.5 H, J ) 3.3 Hz),
3.45, 3.43 (2s, 3 H), 1.48, 1.31 (2s, 6 H); 13C NMR (CDCl3) δ
112.4, 105.6, 105.5, 83.6, 83.4, 81.8, 81.6, 81.2, 79.0, 78.0, 76.7,
70.4, 68.8, 58.3, 26.9, 26.3; MS m/z 281 (M+ + 1), 265, 217.
3-O-Ben zyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfite (8d ). Column chromatography (1:1 ether-
hexane) of the crude product gave 8d (mixture of stereoiso-
mers) (89%) as a syrup: IR (neat) 1455, 1378, 1212, 1164, 1076
13C NMR (CDCl3) δ
111.8, 111.4, 104.8, 104.6, 83.2, 79.2, 77.2, 76.8, 76.2, 75.5, 69.1,
67.4, 56.5, 56.3, 54.4, 54.3, 27.1, 26.8, 26.6.
3-O-Acetyl-1,2-O-isop r op ylid en e-â-D-a ltr ofu r a n ose 5,6-
Cyclic Su lfite (59). Column chromatography (ether-hexane
5:1) of the crude product gave 59 (100%) as a syrup: IR (neat)
1
1749, 1217, 1029 cm-1; H NMR (CDCl3) δ 5.93 (d, 1 H, J )
3.8 Hz), 5.42, 5.33 (2 s, 1 H), 5.15 (ddd, 0.5 H, J ) 10.0, 6.2,
3.7 Hz), 4.81-4.55 (m, 3 H), 4.41 (d, ∼0.5 H, J ) 9.6 Hz), 4.13-
4.00 (m, 0.5 H), 3.94 (d, 0.5 H, J ) 10.0 Hz), 2.11, 2.10 (2 s, 3
H), 1.55, 1.52, 1.31 (3 s, 6 H); 13C NMR (CDCl3) δ 169.5, 112.9,
112.7, 106.3, 86.8, 84.4, 84.3, 80.3, 78.4, 77.3, 77.1, 70.6, 69.2,
26.7, 25.5, 20.8; MS (calcd mass for C11H16O8S + H 309.0644)
obsd m/z 309.0657.
1
cm-1; H NMR (CDCl3) δ 7.34 (m, 5 H), 5.91 (d, 1 H, J ) 3.6
Hz), 5.90 (d, 1 H, J ) 3.4 Hz), 5.16 (dt, 0.5 H, J ) 6.6, 4.9 Hz),
4.80-4.45 (m, 6 H), 4.25 (dd, 0.5 H, J ) 6.6, 3.3 Hz), 4.13 (d,
0.5 H, J ) 3.2 Hz), 4.04 (d, 0.5 H, J ) 3.4 Hz), 1.49, 1.48, 1.31
(3 s, 6 H); 13C NMR (CDCl3) δ 137.2, 136.9, 128.8, 128.7, 128.4,
128.2, 128.0, 127.9, 112.5, 112.4, 105.7, 105.6, 82.6, 82.3, 81.7,
81.4, 81.3, 79.2, 78.1, 76.9, 72.8, 72.7, 70.5, 69.0, 27.0, 26.9,
26.3, 26.3; MS m/z 357 (M+ + 1), 341, 281, 181, 91.
3-O-Ben zyl-2-d eoxy-L-er yth r o-a ld eh yd o-p en tose Dim -
eth yl Aceta l 4,5-Cyclic Su lfite (67). Column chromatog-
raphy (ether-hexane 5:1) of the crude product gave 67 (98%)
as a syrup: IR (neat) 1210, 1125, 1028 cm-1; 1H NMR (CDCl3)
δ 7.34 (m, 5 H), 4.98 (ddd, 0.5 H, J ) 10.5, 6.9, 4.4 Hz), 4.72-
4.47 (m, 5 H), 4.43 (dd, 0.5 H, J ) 8.3, 5.9 Hz), 3.99 (dt, 0.5 H,
J ) 7.3, 4.7 Hz), 3.81 (m, 0.5 H), 3.32, 3.31, 3.28 (3 s, 6 H),
3-Deoxy-1,2-O-isopr opyliden e-r-D-r iboh exofu r an ose 5,6-
Cyclic Su lfite (8e). Column chromatography (ether) of the
crude product gave 8e (85%). The mixture of the two stere-
oisomers could be resolved by column chromatography (ether:
hexane 1:3) using an analytical sample. The first stereoisomer
was a solid that showed the following physical data: mp 66-
1.98-1.80 (m, 2 H);
13C NMR (CDCl3) δ 128.6, 128.3, 128.1,
128.0, 101.5, 101.4, 84.5, 81.6, 75.2, 74.3, 73.6, 73.5, 68.5, 68.2,
53.3, 53.2, 52.8, 35.4, 35.2; MS m/z 285 (M+ + 1 - CH3OH).
Gen er a l P r oced u r e for F or m a tion of Cyclic Su lfa tes
3, 9a ,c-f, 15a ,b, 24, 28, 36, 60, a n d 68. To a solution of the
cyclic sulfites 2, 8a ,c-f, 14a ,b, 59, and 67 (5 mmol) in a
mixture of MeCN (20 mL)/CCl4 (20 mL) was added NaIO4 (1.5
equiv) followed by a catalytic amount of RuCl3‚3H2O and water
(20 mL). The resulting mixture was stirred for 15-60 min at
rt until TLC showed complete disappearance of the starting
material. The mixture was diluted with ether (50 mL/mmol).
The organic layer was washed with water (2 × 100 mL) and
brine (100 mL). The organic solution was dried (Na2SO4) and
filtered. The filtrate was evaporated under reduced pressure
to give the corresponding cyclic sulfate, which was purified
by column chromatography. Compounds 24, 28, and 36 were
obtained from the corresponding diols 23, 27, and 35, respec-
tively, following the general procedures described above for
the synthesis of cyclic sulfites and cyclic sulfates without the
purification of the intermediate cyclic sulfite.
67 °C; [R]D -53° (c 1, chloroform); IR (KBr) 1205, 1024 cm-1
;
1H NMR (CDCl3) δ 5.82 (d, 1 H, J ) 3.6 Hz), 4.79 (pseudo-t, 1
H, J ) 4.2 Hz), 4.66-4.40 (m, 4 H), 2.36 (d, 1 H, J ) 13.6, 4.1
Hz), 1.86 (ddd, 1 H, J ) 13.6, 10.0, 4.8 Hz), 1.51, 1.32 (2s, 6
H); 13C NMR (CDCl3) δ 112.0, 105.8, 83.5, 80.5, 78.2, 69.8, 36.3,
26.9, 26.2; MS m/z 251 (M+ + 1), 235. Anal. Calcd for
C9H14O6S: C, 43.25; H, 5.60; S, 12.80. Found: C, 43.21; H,
5.46; S, 12.42. The second stereoisomer eluted was a solid that
showed the following physical data: mp 45-46 °C; [R]D -64°
(c 1, chloroform); IR (KBr) 1380, 1323, 1258, 1205 cm-1 1H
;
NMR (CDCl3) δ 5.79 (d, 1 H, J ) 3.5 Hz), 4.85-4.71 (m, 3 H),
4.40 (dd, 1 H, J ) 8.6, 4.4 Hz), 4.15 (ddd, 1 H, J ) 10.5, 6.8,
4.5 Hz), 2.26 (dd, 1 H, J ) 13.6, 4.5 Hz), 1.66 (ddd, 1 H, J )
13.6, 10.5, 4.7 Hz), 1.49, 1.30 (2s, 6 H); 13C NMR (CDCl3) δ
111.9, 105.8, 80.9, 80.3, 76.9, 69.3, 36.2, 26.8, 26.1; MS m/z
251 (M+ + 1), 235. Anal. Calcd for C9H14O6S: C, 43.25; H,
5.60; S, 12.80. Found: C, 43.21; H, 5.46; S, 12.52.
(2R)-1-O-Ben zylglycer ol 2,3-Cyclic Su lfa te (3). Column
chromatography (ether-hexane 1:1) of the crude product gave
3 (50%) as a syrup: [R]D +2.4° (c 4, chloroform); IR (neat) 1386,
1211, 1108, 1058, 984 cm-1; 1H NMR (CDCl3) δ 7.40-7.30 (m,
5 H), 5.04 (tt, 1 H, J ) 6.6, 4.9 Hz), 4.69 (dd, 1 H, J ) 8.8, 6.6
Hz), 4.62-4.56 (m, 3 H), 3.76 (d, 2 H, J ) 4.9 Hz); 13C NMR
3-Azid o-3-d e oxy-1,2-O-isop r op ylid e n e -r-D-a llofu r a -
n ose 5,6-Cyclic Su lfite (8f). Column chromatography (ether-
hexane 1:1) of the crude product gave 8f (98%) as a syrup: IR
(neat) 2114, 1377, 1254, 1218, 1163, 1110 cm-1 1H NMR
;
(CDCl3) δ 5.80 (d, 0.5 H, J ) 3.6 Hz), 5.79 (d, 0.5 H, J ) 3.4

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3953
(CDCl3) δ 136.8, 128.7, 128.3, 127.9, 80.0, 73.9, 69.8, 67.5; MS
m/z 244 (M+), 105, 91; MS (calcd mass for C10H12O5S 244.0405)
obsd m/z 244.0401.
mp 62 °C; [R]D -11° (c 1, chloroform); IR (neat) 1389, 1380,
1213, 1111, 1071 cm-1; 1H NMR (CDCl3) δ 5.04 (bdt, 1 H, J )
7.0, 2.2 Hz), 4.75 (dd, 1 H, J ) 8.7, 7.9 Hz), 4.68 (dd, 1 H, J )
8.7, 6.8 Hz), 4.45 (bd, 1 H, J ) 4.8 Hz), 4.14-4.11 (m, 2 H),
3.49, 3.46 (2 s, 6 H), 1.46 (s, 6 H); 13C NMR (CDCl3) δ 111.5,
104.2, 80.6, 76.2, 75.3, 69.7, 56.9, 54.6, 27.1, 26.4; MS (calcd
mass for C10H18O8S + H 299.0801) obsd m/z 299.0798.
3-O-Acetyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfa te (9a ). Column chromatography (ether-hexane
2:1) of the crude product gave 9a (87%) as a solid: mp 142-
144 °C (from ether-hexane); [R]D -45° (c 1, chloroform); IR
(KBr) 1756, 1395, 1214, 1162, 1077, 1060, 1034 cm-1; 1H NMR
(CDCl3) δ 5.90 (d, 1 H, J ) 3.5 Hz), 5.30 (d, 1 H, J ) 3.3 Hz),
5.03 (dt, 1 H, J ) 7.7, 6.4 Hz), 4.80-4.75 (m, 2 H), 4.56 (dd, 1
H, J ) 7.7, 3.3 Hz), 4.55 (d, 1 H, J ) 3.6 Hz), 2.12 (s, 3 H),
1.53, 1.31 (2 s, 6 H); 13C NMR (CDCl3) δ 169.0, 113.3, 105.3,
3-O-Acetyl-1,2-O-isop r op ylid en e-â-D-a ltr ofu r a n ose 5,6-
Cyclic Su lfa te (60). Column chromatography (ether) of the
crude product gave 60 (90%) as a solid: mp 121-122 °C; [R]D
+8°, [R]438 +13.5° (c 1, chloroform); IR (KBr) 1742, 1389, 1212,
1
1021 cm-1; H NMR (CDCl3) δ 5.94 (d, 1 H, J ) 3.7 Hz), 5.30
83.3, 77.3, 76.6, 75.6, 70.3, 26.8, 26.2, 20.8; MS m/z 325 (M+
1), 309, 295, 267. Anal. Calcd for C11H16O9S: C, 40.74; H,
4.97; S, 9.88. Found: C, 41.30; H, 4.97; S, 9.41.
+
(s, 1 H), 5.13 (dt, 1 H, J ) 9.9, 6.1 Hz), 4.78 (dd, 1 H, J ) 9.4,
6.4 Hz), 4.70 (dd, 1 H, J ) 8.4, 6.1 Hz), 4.62 (d, 1 H, J ) 3.7
Hz), 4.34 (d, 1 H, J ) 9.9 Hz), 2.12 (s, 3 H), 1.53, 1.46 (2 s, 6
H); 13C NMR (CDCl3) δ 169.4, 113.0, 106.3, 84.2, 83.7, 78.3,
76.7, 70.2, 26.7, 25.3, 20.7. Anal. Calcd for C11H16O9S: C,
40.74; H, 4.97; S, 9.88. Found: C, 40.92; H, 4.92; S, 9.49.
1,2-O-Isopr opyliden e-3-O-m eth yl-r-D-glu cofu r an ose 5,6-
Cyclic Su lfa te (9c). Column chromatography (ether-hexane
5:1) of the crude product gave 9c (85%) as a solid: mp 83-84
°C; [R]D -43° (c 1, chloroform); IR (Nujol) 1284, 1203, 1164,
1134, 1085, 965 cm-1; 1H NMR (CDCl3) δ 5.91 (d, 1 H, J ) 3.6
Hz), 5.15 (dt, 1 H, J ) 6.6, 6.0 Hz), 4.79 (dd, 1 H, J ) 9.0, 6.7
Hz), 4.71 (dd, 1 H, J ) 9.0, 6.6 Hz), 4.61 (d, 1 H, J ) 3.6 Hz),
4.54 (dd, 1 H, J ) 5.9, 3.4 Hz), 3.88 (d, 1 H, J ) 3.4 Hz), 3.43
(s, 3 H), 1.50, 1.33 (2 s, 6 H); 13C NMR (CDCl3) δ 112.7, 105.6,
3-O-Ben zyl-2-d eoxy-L-er yth r o-a ld eh yd o-p en tose Dim -
eth yl Aceta l 4,5-Cyclic Su lfa te (68). Compound 68 is
obtained as a nonstable product in 97% yield as a syrup being
used directly in the next step without purification by column
1
chromatography: IR (neat) 1386, 1211, 1123, 1053 cm-1; H
NMR (CDCl3) δ 7.35 (m, 5 H), 4.98 (dt, 1 H, J ) 7.0, 4.2 Hz),
4.73-4.58 (m, 4 H), 4.48 (dd, 1 H, J ) 5.8, 5.0 Hz), 4.01 (dt, 1
H, J ) 5.8, 4.0 Hz), 3.31, 3.29 (2 s, 6 H), 1.93-1.86 (m, 2 H);
13C NMR (CDCl3) δ 137.2, 128.8, 128.4, 101.2, 83.0, 73.8, 73.3,
69.2, 53.6, 53.5, 34.2.
83.5, 81.2, 78.4, 78.1, 70.3, 58.1, 26.9, 26.2; MS m/z 297 (M+
1), 281, 239. Anal. Calcd for C10H16O8S: C, 40.54; H, 5.44; S,
10.82. Found: C, 40.18; H, 5.44; S, 10.80.
+
3-O-Ben zyl-1,2-O-isopr opyliden e-r-D-glu cofu r an ose 5,6-
Cyclic Su lfa te (9d ). Column chromatography (ether-hexane
1:1) of the crude product gave 9d (83.0%) as a solid: mp 87-
88 °C; [R]D -48° (c 1, chloroform); IR (KBr) 1383, 1270, 1210,
2,4-O-Eth ylid en e-D-er yth r itol 1,3-Cyclic Su lfa te (24).
Compound 23133 was transformed via the cyclic sulfite into the
cyclic sulfate 24 following the general procedure described
above without purification of the cyclic sulfite. Column
chromatography (ether-hexane 1:1) of the crude product gave
24 (48% overall yield from 23) as a solid: mp 81-82 °C; [R]D
+6° (c 1, chloroform); IR (KBr) 1322, 1207, 1164, 1119, 1041
cm-1; 1H NMR (CDCl3) δ 4.82 (q, 1 H, J ) 5.0 Hz), 4.67 (dt, 1
H, J ) 10.2, 5.0 Hz), 4.66 (t, 1 H, J ) 10.6 Hz), 4.52 (dd, 1 H,
J ) 10.5, 5.0 Hz), 4.24 (dd, 1 H, J ) 10.5, 5.0 Hz), 3.98 (ddd,
1 H, J ) 10.8, 9.6, 5.0 Hz), 3.72 (t, 1 H, J ) 10.4 Hz), 1.37 (d,
3 H, J ) 5.0 Hz); 13C NMR (CDCl3) δ 100.8, 75.3, 72.6, 71.0,
1
1075, 985 cm-1; H NMR (CDCl3) δ 7.40-7.23 (m, 5 H), 5.93
(d, 1 H, J ) 3.6 Hz), 5.12 (q, 1 H, J ) 6.5 Hz), 4.78 (dd, 1 H,
J ) 9.1, 6.5 Hz), 4.72-4.50 (m, 4 H), 4.62 (d, 1 H, J ) 3.6 Hz),
4.10 (d, 1 H, J ) 3.4 Hz), 1.49, 1.32 (2 s, 6 H); 13C NMR (CDCl3)
δ 136.5, 128.9, 128.6, 128.1, 112.8, 105.7, 82.1, 81.3, 78.6, 77.8,
72.7, 70.4, 27.0, 26.3. Anal. Calcd for C16H20O8S: C, 51.56;
H, 5.41; S, 8.61. Found: C, 51.12; H, 5.44; S, 8.63.
3-Deoxy-1,2-O-isopr opyliden e-r-D-r iboh exofu r an ose 5,6-
Cyclic Su lfa te (9e). Column chromatography (ether) of the
crude product gave 9e (72%) as a solid: mp 100-102 °C; [R]D
-48° (c 1, chloroform); IR (KBr) 1388, 1209, 1049, 1016, 983
66.8, 20.03; MS m/z 211 (M+ + 1), 195 (M+ - CH3), 167 (M+
-
C2H3O); MS (calcd mass for C6H10O6 + H 211.0276) obsd m/z
1
cm-1; H NMR (CDCl3) δ 5.83 (d,1 H, J ) 3.5 Hz), 4.87-4.75
211.0270.
(m, 3 H), 4.61 (dd, 1 H, J ) 8.7, 6.2 Hz), 4.42 (ddd, 1 H, J )
10.4, 6.2, 4.4 Hz), 2.37 (dd, 1 H, J ) 13.5, 4.6 Hz), 1.80 (ddd,
1 H, J ) 13.5, 10.4, 4.7 Hz), 1.52, 1.33 (2 s, 6 H); 13C NMR
(CDCl3) δ 112.3, 105.9, 81.5, 80.7, 76.4, 70.4, 35.7, 26.9, 26.1;
MS m/z 251 (M+ - CH3). Anal. Calcd for C9H14O7S: C, 40.60;
H, 5.30; S, 12.04. Found: C, 40.75; H, 4.92; S, 12.35.
Meth yl 2,3-d i-O-ben zyl-r-D-glu cop yr a n osid e 4,6-Cyclic
Su lfa te (28). Compound 27 was transformed via the cyclic
sulfite into the cyclic sulfate following the general procedure
described above without purification of the cyclic sulfite.
Column chromatography (ether) of the crude product gave 28
(58% overall yield from 27) as a solid: mp 93-96 °C; [R]D +18°
3-Azid o-3-d e oxy-1,2-O-isop r op ylid e n e -r-D-a llofu r a -
n ose 5,6-Cyclic Su lfate (9f). Column chromatography (ether-
hexane 5:1) of the crude product gave 9f (83%) as a solid: mp
130 °C; [R]D +119° (c 1, chloroform); IR (KBr) 2116, 1387, 1256,
(c 1, chloroform); IR (KBr) 1402, 1174, 1112, 1058, 991 cm-1
;
1H NMR (CDCl3) δ 7.40-7.30 (m, 10 H), 4.82 (bs, 2 H), 4.74
(AB system, 2 H, J ) 12.1 Hz, δν ) 36.0 Hz), 4.60 (t, 1 H, J )
10.7 Hz), 4.57 (t, 1 H, J ) 9.5 Hz), 4.56 (d, 1 H, J ) 3.6 Hz),
4.47 (dd, 1 H, J ) 10.4, 5.1 Hz), 4.15 (dt, 1 H, J ) 10.7, 5.1
Hz), 4.04 (t, 1 H, J ) 9.3 Hz), 3.52 (dd, 1 H, J ) 9.3, 3.8 Hz),
3.42 (s, 3 H); 13C NMR (CDCl3) δ 137.8, 137.6, 128.7, 128.5,
128.3, 128.1, 128.0, 99.3, 84.6, 78.7, 77.0, 60.5, 75.6, 74.1, 72.2,
56.1; MS m/z 435 (M+ - 1), 345, 181. Anal. Calcd for
C21H24O8S: C, 57.79; H, 5.54; S, 7.34. Found: C, 57.97; H,
5.42; S, 7.05.
1
1207 cm-1; H NMR (CDCl3) δ 5.82 (d, 1 H, J ) 3.6 Hz), 5.06
(dt, 1 H, J ) 6.8, 4.8 Hz), 4.82 (dd, 1 H, J ) 6.5, 3.7 Hz), 4.80-
4.73 (m, 2 H), 4.21 (dd, 1 H, J ) 9.3, 4.8 Hz), 3.68 (dd, 1 H, J
) 9.3, 4.7 Hz), 1.58, 1.38 (2 s, 6 H); 13C NMR (CDCl3) δ 114.2,
104.3, 80.2, 79.9, 76.4, 68.9, 61.7, 26.6, 26.4; MS m/z 292 (M+
- CH3), 249. Anal. Calcd for C9H13N3O7S: C, 35.18; H, 4.26;
N, 13.67; S, 10.43. Found: C, 35.33; H, 4.17; N, 13.29; S, 10.09.
2-Aceta m id o-2-d eoxy-3,4-O-isop r op ylid en e-a ld eh yd o-
D-glu cose Dim eth yl Aceta l 5,6-Cyclic Su lfa te (15a ). Col-
umn chromatography (ethyl acetate) of the crude product gave
15a (95%) as a solid: mp 124-125 °C; [R]D -8°, [R]436 -16° (c
3,4-Di-O-ben zyl-D-m an n itol 1,2:5,6-Cyclic Disu lfate (36).
Compound 35134 was transformed via the cyclic sulfite into the
cyclic sulfate following the general procedure described above
without purification of the cyclic sulfite. Column chromatog-
raphy (ether-hexane 1:1) of the crude product gave 36 (94%
overall yield from 35) as a solid: mp 112 °C; [R]D +7°, [R]436
2, chloroform); IR (Nujol) 3420, 1666, 1533 cm-1 1H NMR
;
(CDCl3) δ 5.84 (d, 1 H, J ) 8.9 Hz), 4.98 (dt, 1 H, J ) 6.4, 5.5
Hz), 4.80 (dd, 1 H, J ) 9.1, 6.3 Hz), 4.73 (dd, 1 H, J ) 9.1, 6.7
Hz), 4.41 (d, 1 H, J ) 5.2 Hz), 4.30-4.25 (m, 2 H), 4.05 (dd, 1
H, J ) 7.5, 5.3 Hz), 3.41, 3.36 (2 s, 6 H), 2.03 (s, 3 H, MeCO),
1.39, 1.38 (2 s, 6 H); 13C NMR (CDCl3) δ 170.4, 110.7, 103.2,
80.4, 76.2, 76.1, 69.5, 55.8, 53.9, 50.1, 27.0, 26.9, 23.3; MS m/z
370 (M+ + 1), 338; MS (calcd mass for C13H23NO9S + H
370.1172) obsd m/z 370.1186.
+13° (c 1, chloroform); IR (KBr) 1382, 1208, 1101, 1049 cm-1
;
1H NMR (CDCl3) δ 7.41-7.26 (m, 10 H), 4.70 (AB system, 4
H, J ) 11.0 Hz, δν ) 53.3 Hz), 4.87-4.78 (m, 4 H), 4.50 (dd,
2 H, J ) 7.0, 4.5 Hz), 4.20 (bs, 2 H); 13C NMR (CDCl3) δ 135.7,
129.4, 129.2, 129.0, 82.2, 76.9, 75.7, 69.1; MS m/z 391 (M+
+
2,3-O-Isop r op ylid en e-a ld eh yd o-D-xylose Dim eth yl Ac-
eta l 4,5-Cyclic Su lfa te (15b). Column chromatography
(ethyl acetate) of the crude product gave 15b (94%) as a solid:
(133) Baker, R.; McDonald, D. L. J . Am. Chem. Soc. 1960, 32, 2301.
(134) J urzak, J .; Bauer, T.; Chmielewski, M. Carbohydr. Res. 1987,
164, 493.

3954 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
1
1 - SO4), 315, 269, 189, 147. Anal. Calcd for C20H22O10S2:
C, 49.37; H, 5.56; S, 13.18. Found: C, 49.47; H, 5.58; S, 13.22.
Gen er a l P r oced u r e for th e Op en in g of Cyclic Su lfa tes
w ith th e P ota ssiu m Sa lt of Th ioa ceta te, Th iocya n a te,
a n d Selen ocya n a te An ion s. To a solution of the cyclic
sulfate 3, 9a ,c-f, 15a ,b, 24, 28, 36, 60, or 68 (1 equiv) in dry
acetone (20 mL) was added the nucleophile (KSAc, KSCN, or
KSeCN) (1.1 equiv). The resulting solution or suspension was
then stirred at rt until no cyclic sulfate remained (TLC). The
solution was then concentrated, and the crude product was
purified by chromatography on silica gel.
1224 cm-1; H NMR (DMSO-d6) δ 5.73 (d, 1 H, J ) 3.7 Hz),
4.69 (t, 1 H, J ) 4.1 Hz), 4.19-10 (m, 2 H), 3.22 (dd, 1 H, J )
13.4, 4.7 Hz), 3.14 (dd, 1 H, J ) 13.4, 4.4 Hz), 2.31 (s, 3 H),
1.96 (dd, 1 H, J ) 14.0, 4.4 Hz), 1.74 (ddd, 1 H, J ) 14.0, 9.8,
4.1 Hz), 1.36, 1.23 (2 s, 6 H); 13C NMR (DMSO-d6) δ 195.0,
110.3, 105.1, 79.8, 77.8, 75.0, 35.1, 30.5, 30.4, 26.7, 26.3; MS
(FAB) m/z 419 (M+ + K), 403 (M+ + Na). Anal. Calcd for
C11H17O8S2K‚H2O: C, 33.16; H, 4.81; S, 16.09. Found: C,
33.29; H, 4.51; S, 15.71.
6-S-Acet yl-3-a zid o-3-d eoxy-1,2-O-isop r op ylid en e-5-O-
su lfo-6-th io-r-D-a llofu r a n ose P ota ssiu m Sa lt (10f). Col-
umn chromatography (methanol-chloroform 1:3) of the crude
product gave 10f (99%) as a solid: mp 195-198 °C dec; [R]D
+82° (c 1, methanol); IR (KBr) 3466, 2104, 1681, 1268, 1232,
(2S)-3-S-Acetyl-1-(ben zyloxy)-2-h ydr oxy-3-th iopr opan e-
2-O-su lfon ic Acid P ota ssiu m Sa lt (4). Column chromatog-
raphy (methanol-chloroform 1:3) of the crude product gave 4
(93%) as a hygroscopic syrup: [R]D +13° (c 1.6, methanol); IR
1
1020 cm-1; H NMR (DMSO-d6) δ 5.77 (d, 1 H, J ) 3.6 Hz),
1
(neat) 1736, 1236, 1099, 1029 cm-1; H NMR (CDCl3) δ 7.26
4.76 (t, 1 H, J ) 4.3 Hz), 4.35-4.22 (m, 2 H), 3.61 (dd, 1 H, J
) 9.1, 4.9 Hz), 3.20 (d, 1 H, J ) 13.8, 4.6 Hz), 3.07 (d, 1 H, J
) 13.8, 5.8 Hz), 2.31 (s, 3 H), 1.42, 1.28 (2 s, 6 H); 13C NMR
(DMSO-d6) δ 195.0, 112.1, 104.0, 80.1, 77.8, 73.8, 60.5, 30.4,
29.7, 26.6, 26.3. Anal. Calcd for C11H16N3O8S2K‚H2O: C,
30.06; H, 4.13; N, 9.56; S, 14.83. Found: C, 30.45; H, 3.75; N,
9.45; S, 14.83.
(bs, 5 H), 4.70 (m, 1 H), 4.48 (AB system, 2 H, J ) 12.3 Hz, δν
) 18.0 Hz), 3.61 (m, 2 H), 3.41 (bd, 1 H, J ) 13.5 Hz), 3.20
(dd, 1 H, J ) 13.5, 7.7 Hz), 2.21 (s, 3 H); 13C NMR (CDCl3) δ
197.9, 137.9, 128.4, 128.0, 127.7, 76.6, 73.2, 69.4, 30.5, 29.5;
MS (FAB) m/z 379 (M+ - 2 H + Na).
(2S)-1-(Ben zyloxy)-3-S-cyan o-2-h ydr oxy-3-th iopr opan e-
2-O-su lfon ic Acid P ota ssiu m Sa lt (5). Column chromatog-
raphy (methanol-chloroform 1:3) of the crude product gave 5
(95.5%) as a hygroscopic syrup: [R]D +2.5° (c 3.4, methanol);
IR (neat) 2159, 1218, 1093, 1025 cm-1; 1H NMR (CDCl3) δ 7.25
(bs, 5 H), 4.90 (bs, 1 H), 4.40 (bs, 2 H), 3.69 (bs, 2 H), 3.43 (bs,
1 H), 3.19 (bs, 1 H); (DMSO-d6) δ 7.36 (m, 5 H), 4.52 (bs, 2 H),
4.45 (m, 1 H), 3.69 (dd, 1 H, J ) 10.1, 4.3 Hz), 3.60 (dd, 1 H,
J ) 10.1, 6.2 Hz), 3.46 (dd, 1 H, J ) 13.2, 5.2 Hz), 3.36 (dd, 1
H, J ) 13.3, 5.4 Hz); 13C NMR (CDCl3) δ 137.4, 128.6, 128.1,
114.1, 75.9, 73.4, 68.5, 34.5; MS (FAB) m/z 380 (M+ + K), 364
(M+ + Na), 348 (M+ - K + 2 Na).
3-O-Acet yl-6-S-cya n o-1,2-O-isop r op ylid en e-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu n Sa lt (11a ). Crystal-
lization from the reaction mixture gave 11a (94%) as a solid:
mp 238 °C dec; [R]D -68° (c 1, methanol); IR (KBr) 2163, 1734,
1252, 1222, 1026 cm-1; H NMR (DMSO-d6) δ 5.87 (d, 1 H, J
1
) 3.7 Hz), 5.01 (d, 1 H, J ) 3.0 Hz), 4.59 (dt, 1 H, J ) 8.0, 4.0
Hz), 4.52 (d, 1 H, J ) 3.7 Hz), 4.29 (dd, 1 H, J ) 8.2, 2.9 Hz),
3.71 (dd, 1 H, J ) 13.5, 3.9 Hz), 3.33 (dd, 1 H, J ) 13.5, 3.9
Hz), 2.00 (s, 3 H), 1.43, 1.24 (2 s, 6 H); 13C NMR (DMSO-d6) δ
169.3, 113.2, 111.5, 104.4, 82.3, 77.4, 74.5, 69.5, 36.6, 26.4, 26.0,
20.6; MS (FAB) m/z 460 (M+ + K), 444 (M+ + Na). Anal.
Calcd for C12H16NO9S2K: C, 34.20; H, 3.83; N, 3.32; S, 15.21.
Found: C, 34.17; H, 3.92; N, 3.34; S, 15.69.
3-O-Acetyl-6-S-a cetyl-1,2-O-isop r op ylid en e-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu m Sa lt (10a ). Column
chromatography (methanol-chloroform 1:3) of the crude prod-
uct gave 10a (97%) as a solid: mp 163-164 °C dec; [R]D -29°
6-S-Cya n o-1,2-O-isop r op ylid en e-3-O-m eth yl-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu m Sa lt (11c). Column
chromatography (methanol-chloroform 1:3) of the crude prod-
uct gave 11c (82%) as a solid: mp 170 °C dec; [R]D -33° (c 1,
methanol); IR (KBr) 2165, 1385, 1375, 1252, 1233, 1116, 1080,
1
(c 1, water); IR (KBr) 1737, 1693, 1252, 1232 cm-1; H NMR
(DMSO-d6) δ 5.84 (d, 1 H, J ) 3.7 Hz), 4.96 (d, 1 H, J ) 2.6
Hz), 4.57 (ddd, 1 H, J ) 8.0, 4.8, 4.0 Hz), 4.48 (d, 1 H, J ) 3.8
Hz), 4.18 (dd, 1 H, J ) 8.0, 2.8 Hz), 3.47 (dd, 1 H, J ) 13.5,
4.0 Hz), 3.15 (dd, 1 H, J ) 13.5, 4.8 Hz), 2.31 (s, 3 H), 1.99 (s,
3 H), 1.40, 1.24 (2 s, 6 H); 13C NMR (DMSO-d6) δ 194.8, 169.6,
113.3, 104.3, 82.4, 78.2, 74.9, 70.8, 31.4, 30.5, 26.5, 26.2, 20.8;
HRMS (FAB) calcd for C13H19O10S2K + K 476.9694 (M + K)+,
found 476.9714.
1023 cm-1 1H NMR (DMSO-d6) δ 5.79 (d, 1 H, J ) 3.6 Hz,
;
H-1), 4.61 (d, 1 H, J ) 3.7 Hz), 4.58 (m, 1 H), 4.24 (dd, 1 H, J
) 6.3, 3.1 Hz), 3.68 (d, 1 H, J ) 3.0 Hz), 3.60 (dd, 1 H, J )
13.2, 3.4 Hz), 3.34 (s, 3 H), 3.25 (dd, 1 H, J ) 13.2, 5.1 Hz),
1.38, 1.24 (2 s, 6 H); 13C NMR (DMSO-d6) δ 113.7, 111.1, 104.4,
82.8, 80.8, 79.4, 70.6, 57.6, 36.7, 26.6, 26.2. Anal. Calcd for
C11H16NO8S2K‚H2O: C, 32.11; H, 4.41; N, 3.41; S, 15.58.
Found: C, 32.42; H, 4.57; N, 3.24; S, 15.24.
6-S-Acetyl-1,2-O-isop r op ylid en e-3-O-m eth yl-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu m Sa lt (10c). Column
chromatography (methanol-chloroform 1:4) of the crude prod-
uct gave 10c (87%) as a solid: mp 164 °C; [R]D -25° (c 1,
3-O-Ben zyl-6-S-cya n o-1,2-O-isop r op ylid en e-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu m Sa lt (11d ). Column
chromatography (methanol-chloroform 1:3) of the crude prod-
uct gave 11d (100%) as a hygroscopic solid: mp 105-106 °C;
1
methanol)); IR (KBr) 1685, 1218, 1115, 1087, 1022 cm-1; H
NMR (DMSO-d6) δ 5.78 (d, 1 H, J ) 3.7 Hz), 4.57 (d,1 H, J )
3.8 Hz), 4.53 (dt, 1 H, J ) 6.0, 3.7 Hz), 4.15 (dd, 1 H, J ) 6.4,
2.9 Hz), 3.64 (d,1 H, J ) 3.0 Hz), 3.41 (dd, 1 H, J ) 13.4, 3.7
Hz), 3.32 (s, 3 H), 3.04 (dd,1 H, J ) 13.4, 6.1 Hz), 2.28 (s, 3
H), 1.37, 1.25 (2 s, 6 H); 13C NMR (DMSO-d6) 195.1, 110.8,
104.3, 82.9, 80.8, 80.0, 70.5, 57.3, 31.3, 30.4, 26.6, 26.2. Anal.
Calcd for C12H19O9S2K‚H2O: C, 33.64; H, 4.94. Found: C,
33.35; H, 4.76.
6-S-Acetyl-3-O-ben zyl-1,2-O-isop r op ylid en e-5-O-su lfo-
6-th io-r-D-glu cofu r a n ose P ota ssiu m Sa lt (10d ). Column
chromatography (methanol-chloroform 1:5) of the crude prod-
uct gave 10d (100%) as a solid: mp 105-106 °C; [R]D -15° (c
1, methanol); IR (KBr) 1691, 1260, 1219, 1075 cm-1; 1H NMR
(DMSO-d6) δ 7.45-7.25 (m, 5 H), 5.80 (d, 1 H, J ) 3.4 Hz),
4.70-4.50 (m, 4 H), 4.18 (dd, 1 H, J ) 6.0, 2.5 Hz), 3.90 (bs, 1
H), 3.47 (dd, 1 H, J ) 13.4, 3.6 Hz), 3.11 (dd,1 H, J ) 13.4, 5.5
Hz), 2.28 (s, 3 H), 1.37, 1.24 (2 s, 6 H); 13C NMR (DMSO-d6) δ
195.0, 138.1, 128.2, 128.0, 127.5, 110.9, 104.3, 81.5, 80.9, 79.9,
71.3, 70.6, 31.4, 30.4, 26.6, 26.2; MS (FAB) m/z 525 (M+ + K),
509 (M+ + Na), 493 (M+ - K + 2 Na). Anal. Calcd for
C18H23O9S2K: C, 44.44; H, 4.76. Found: C, 44.47; H, 4.99.
6-S-Acet yl-3-d eoxy-1,2-O-isop r op ylid en e-5-O-su lfo-6-
th io-r-D-r iboh exofu r a n ose P ota ssiu m Sa lt (10e). Crystal-
lization from the reaction mixture gave 10e (80%) as a solid:
mp 217-218 °C; [R]D +1° (c 1, methanol); IR (KBr) 1694, 1238,
[R]D
-31° (c 1, water); IR (KBr) 1259, 1222, 1163, 1081, 1015
cm-1; 1H NMR (DMSO-d6) δ 7.45-7.22 (m, 5 H), 5.82 (d, 1 H,
J ) 3.6 Hz), 4.71 (m, 1 H), 4.68 (d, 1 H, J ) 3.6 Hz), 4.61 (bs,
2 H), 4.28 (dd,1 H, J ) 6.6, 2.9 Hz), 3.94 (d, 1 H, J ) 3.0 Hz),
3.60 (dd, 1 H, J ) 13.4, 3.6 Hz), 3.31 (dd, 1 H, J ) 13.3, 4.7
Hz), 1.40, 1.25 (2 s, 6 H);
13C NMR (DMSO-d6) 137.7, 128.1,
128.0, 127.5, 113.5, 111.1, 104.3, 81.4, 80.5, 79.1, 71.4, 70.3,
36.6, 26.5, 26.1; MS (FAB) m/z 508 (M + K)+, 492 (M + Na)+,
476 (M - K + 2 Na)+. Anal. Calcd for C17H20NO8S2K‚H2O:
C, 41.89; H, 4.52; N, 2.87; S, 13.14. Found: C, 41.42; H, 4.30;
N, 3.11; S, 13.06.
6-S-Cya n o-3-d eoxy-1,2-O-isop r op ylid en e-5-O-su lfo-6-
th io-r-D-r iboh exofu r a n ose P ota ssiu m Sa lt (11e). Column
chromatography (methanol-chloroform 1:4) of the crude prod-
uct gave 11e (80%) as a solid: mp 225 °C dec; [R]D -9° (c 1,
methanol); IR (KBr) 1242, 1222, 1018 cm-1; 1H NMR (DMSO-
d6) δ 5.75 (d, 1 H, J ) 4.6 Hz), 4.72 (t, 1 H, J ) 3.8 Hz), 4.31-
4.21 (m, 2 H), 3.52 (dd, 1 H, J ) 13.3, 4.1 Hz), 3.37 (dd, 1 H,
J ) 13.3, 4.6 Hz), 2.04 (dd, 1 H, J ) 14.4, 4.6 Hz), 1.75 (ddd,
1 H, J ) 14.4, 9.6, 4.5 Hz), 1.40, 1.24 (2 s, 6 H); 13C NMR
(DMSO-d6) δ 113.8, 110.6, 105.2), 79.8, 77.2, 74.8, 35.8, 35.4,
26.7, 26.2; MS (FAB) m/z 370 (M - K + 2 Na)+. Anal. Calcd
for C10H14O7NS2K: C, 33.05; H, 3.88; N, 3.85. Found: C, 33.25;
H, 4.23; N, 3.69.

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3955
3-Azid o-6-S-cya n o-3-d eoxy-1,2-O-isop r op ylid en e-5-O-
su lfo-6-th io-r-D-a llofu r a n ose P ota ssiu m Sa lt (11f). Col-
umn chromatography (methanol-chloroform 1:3) of the crude
product gave 11f (99%) as a solid: mp 118-121 °C; [R]D +75°
(c 1, methanol); IR (KBr) 3486, 2161, 2113, 1376, 1235, 1011,
30.4. Anal. Calcd for C23H27O9S2K: C, 50.18; H, 4.95.
Found: C, 49.82; H, 5.14.
3-O-Acetyl-6-Se-cya n o-1,2-O-isop r op ylid en e-6-selen o-
5-O-su lfo-r-D-glu cofu r a n ose P ota ssiu m Sa lt (31a ). Col-
umn chromatography (methanol-chloroform 1:3) of the crude
product gave 31a (97%) as a solid: mp 160 °C dec; [R]D -65°
886 cm-1 1H NMR (DMSO-d6) δ 5.77 (d, 1 H, J ) 3.5 Hz),
;
1
4.77 (t, 1 H, J ) 4.4 Hz), 4.38 (m, 1 H), 4.31 (dd, 1 H, J ) 9.5,
4.4 Hz), 3.68 (dd, 1 H, J ) 9.5, 4.8 Hz), 3.54 (dd, 1 H, J )
13.4, 4.1 Hz), 3.30 (d, 1 H, J ) 13.4, 5.9 Hz), 1.44, 1.29 (2 s, 6
H); 13C NMR (DMSO-d6) δ 113.6, 112.3, 104.1, 80.1, 77.6, 73.5,
60.6, 34.8, 26.5, 26.4. Anal. Calcd for C10H13N4O7S2K‚H2O:
C, 28.43; H, 3.58; N, 13.26; S, 15.18. Found: C, 28.89; H, 3.45;
N, 13.47; S, 14.98.
(c 1, methanol); IR (KBr) 2160, 1743 cm-1; H NMR (DMSO-
d6) δ 5.89 (d, 1 H, J ) 3.6 Hz), 5.01 (d, 1 H, J ) 2.8 Hz), 4.57
(m, 1 H), 4.53 (d, 1 H, J ) 3.6 Hz), 4.26 (dd, 1 H, J ) 8.2, 3.0
Hz), 3.63 (dd, 1 H, J ) 12.1, 4.3 Hz), 3.43 (dd, 1 H, J ) 12.1,
5.0 Hz), 2.01 (s, 3 H), 1.44, 1.25 (2 s, 6 H); 13C NMR (DMSO-
d6) δ 169.4, 111.6, 104.5, 82.5, 78.7, 74.6, 70.5, 32.2, 26.5, 26.1,
20.7. Anal. Calcd for C12H16NO9SeSK: C, 30.77; H, 3.44; N,
2.99. Found: C, 30.76; H, 4.01; N, 2.72.
6-Se-Cya n o-1,2-O-isop r op ylid en e-3-O-m eth yl-6-selen o-
5-O-su lfo-r-D-glu cofu r a n ose P ota ssiu m Sa lt (31c). Col-
umn chromatography (methanol-chloroform 1:3) of the crude
product gave 31c (90%) as a hygroscopic solid: mp 102-104
°C dec; [R]D -3°, [R]436 -7° (c 1, methanol); IR (KBr) 1221,
1078, 1015, 946 cm-1; 1H NMR (DMSO-d6) δ 5.75 (d, 1 H, J )
3.6 Hz), 4.57 (d, 1 H, J ) 3.7 Hz), 4.56 (m, 1 H), 4.20 (dd, 1 H,
J ) 7.7, 2.6 Hz), 3.61 (d, 1 H, J ) 2.6 Hz), 3.32 (s, 3 H), 3.22
(dd, 1 H, J ) 13.0, 3.7 Hz), 2.68 (dd, 1 H, J ) 13.0, 4.0 Hz),
1.38, 1.24 (2 s, 6 H); 13C NMR (DMSO-d6) δ 110.9, 104.3, 82.5,
81.1, 79.9, 71.1, 57.5, 32.6, 26.6, 26.2.
2-Aceta m id o-6-S-a cetyl-2-d eoxy-3,4-O-isop r op ylid en e-
5-O-su lfo-6-th io-a ld eh yd o-D-glu cose Dim eth yl Aceta l P o-
ta ssiu m Sa lt (16a ). Column chromatography (methanol-
chloroform 1:3) of the crude product gave 16a (95%) as a
hygroscopic solid: mp 120 °C; [R]D -2.4° (c 0.5, water); IR
(KBr) 3580, 1665, 1541, 1244, 1067 cm-1 1H NMR (DMSO-
;
d6) δ 7.48 (d, 1 H, J ) 9.7 Hz), 4.28 (d, 1 H, J ) 7.0 Hz), 4.28-
4.08 (m, 3 H), 3.70 (t, 1 H, J ) 7.0 Hz), 3.30-3.10 (m, 2 H),
3.22, 3.21 (2 s, 6 H), 2.29, 1.84 (2 s, 6 H), 1.30, 1.28 (2 s, 6 H);
13C NMR (DMSO-d6) δ 195.1, 169.3, 109.2, 102.6, 77.5, 77.2,
74.9, 53.5, 52.6, 50.3, 30.9, 30.5, 27.2, 27.1, 22.7; MS (FAB)
calcd for C15H26NO10S2K + H 484.0713, found 484.0685.
5-S-Acetyl-2,3-O-isop r op ylid en e-4-O-su lfo-5-th io-a ld e-
h yd o-D-xylose Dim eth yl Aceta l P ota ssiu m Sa lt (16b).
Column chromatography (methanol-chloroform 1:3) of the
crude product gave 16b (72%) as a solid: mp 140-142 °C; [R]D
3-O-Ben zyl-6-Se-cya n o-1,2-O-isop r op ylid en e-6-selen o-
5-O-su lfo-r-D-glu cofu r a n ose P ota ssiu m Sa lt (31d ). Col-
umn chromatography (chloroform-methanol 5:1) of the crude
product gave 31d as a solid (100%): mp 105-107 °C dec; [R]D
-30° (c 1, methanol); IR (KBr) 2165, 1375, 1259, 1221, 1161,
-18° (c 1, methanol); IR (KBr) 1685, 1252, 1086, 1003 cm-1
;
1
1107, 1087, 1005 cm-1; H NMR (DMSO-d6) δ 7.41-7.25 (m,
1H NMR (DMSO-d6) δ 4.30 (d, 1 H, J ) 5.8 Hz), 4.23 (t, 1 H,
J ) 5.8 Hz), 4.07 (ddd, 1 H, J ) 9.6, 4.8, 1.6 Hz), 3.98 (dd, 1
H, J ) 5.7, 1.6 Hz), 3.35 (dd, 1 H, J ) 12.7, 4.8 Hz), 3.30, 3.28
(2 s, 6 H), 3.01 (dd, 1 H, J ) 12.7, 9.6 Hz), 2.31 (s, 3 H), 1.30,
1.28 (2 s, 6 H); 13C NMR (DMSO-d6) δ 109.5, 104.7, 77.4, 75.4,
72.3, 55.0, 53.7, 30.5, 29.8, 27.3, 26.7; MS (FAB) m/z 451 (M
+ K)+, 435 (M + Na)+, 419 (M - K + 2 Na)+.
5 H), 5.83 (d, 1 H, J ) 3.6 Hz), 4.68 (d, 1 H, J ) 3.7 Hz), 4.67
(m, 1 H), 4.62 (bs, 2 H), 4.22 (dd, 1 H, J ) 6.9, 2.9 Hz), 3.93 (d,
1 H, J ) 3.0 Hz), 3.66 (dd, 1 H, J ) 12.2, 4.2 Hz), 3.42 (dd, 1
H, J ) 12.2, 4.6 Hz), 1.40, 1.25 (2 s, 6 H); 13C NMR (DMSO-
d6) δ 137.8, 128.2, 128.1, 127.6, 111.2, 104.8, 104.1, 81.5, 80.4,
80.0, 71.5, 70.8, 32.4, 26.7, 26.2; MS (FAB) m/z 516 (M+). Anal.
Calcd for C17H20NO8SeSK‚2H2O: C, 36.96; H, 4.38; N, 2.54;
S, 5.80. Found: C, 37.26; H, 4.70; N, 1.91; S, 5.56.
2-Aceta m id o-6-S-cya n o-2-d eoxy-3,4-O-isop r op ylid en e-
5-O-su lfo-6-th io-a ld eh yd o-D-glu cose Dim eth yl Aceta l P o-
ta ssiu m Sa lt (17a ). Column chromatography (methanol-
chloroform 1:5) of the crude product gave 17a (98%) as a
solid: mp 176-177 °C; [R]D -16° (c 1, methanol); IR (Nujol)
3347, 2070, 1653, 1541, 1274, 1073 cm-1; 1H NMR (DMSO-d6)
δ 7.60 (d, 1 H, J ) 9.0 Hz), 4.14 (m, 1 H), 4.12 (d, 1 H, J ) 7.1
Hz), 4.08 (dd, 1 H, J ) 6.6, 2.7 Hz), 3.95 (ddd, 1 H, J ) 9.0,
7.0, 2.5 Hz), 3.62 (t, 1 H, J ) 7.3 Hz), 3.37 (dd, 1 H, J ) 13.2,
5.0 Hz), 3.17 (dd, 1 H, J ) 13.2, 3.6 Hz), 3.04, 3.02 (2 s, 6 H),
1.66 (s, 3 H), 1.14, 1.10 (2 s, 6 H); 13C NMR (DMSO-d6) δ 169.4,
113.5, 109.4, 102.4, 77.6, 76.2, 74.6, 53.3, 52.6, 50.1, 36.2, 27.1,
27.0, 22.6. Anal. Calcd for C14H23N2O9S2K: C, 36.05; H, 4.97;
N, 6.01. Found: C, 35.90; H, 5.05; N, 5.90.
6-Se-Cya n o-3-d eoxy-1,2-O-isop r op ylid en e-6-selen o-5-
O-su lfo-r-D-r iboh exofu r a n ose P ota ssiu m Sa lt (31e). Col-
umn chromatography (methanol-chloroform 1:3) of the crude
product gave 31e (100%) as a non stable solid: mp 105-110
°C dec; [R]D -13° (c 0.5, methanol); IR (KBr) 2071, 1248, 1209,
1
1160, 1006, 1065, 1023 cm-1; H NMR (DMSO-d6) δ 5.74 (dd,
1 H, J ) 3.3 Hz), 4.71 (t, 1 H, J ) 3.7 Hz), 4.25 (m, 2 H), 3.04
(m, 2 H), 2.04 (m, 1 H), 1.75 (m, 1 H), 1.39, 1.23 (2 s, 6 H); 13
C
NMR (DMSO-d6) δ 110.6, 105.2, 105.2, 79.8, 78.4, 75.1, 35.2,
31.0, 26.7, 26.2, 20.7.
3-Azid o-6-Se-cya n o-3-d eoxy-1,2-O-isop r op ylid en e-6-se-
len o-5-O-su lfo-r-D-a llofu r a n ose P ota ssiu m Sa lt (31f). Col-
umn chromatography (methanol-chloroform 1:5) of the crude
product gave 31f (100%) as a hygroscopic foam: [R]D +42° (c
(2R,4R,5R)-4-[(Acetylth io)m eth yl]-2-m eth yl-5-O-su lfo-
1,3-d ioxa n e P ota ssiu m Sa lt (25). Column chromatography
(methanol-chloroform 1:4) of the crude product gave 25 (86%)
as a solid: mp 81-82 °C; [R]D +6° (c 1, methanol); IR (KBr)
1.5, methanol); IR (neat) 2114, 1259, 1112, 1071, 1022 cm-1
;
1H NMR (DMSO-d6) δ 5.77 (d, 1 H, J ) 3.5 Hz), 4.77 (pseudo-
t, 1 H, J ) 4.1 Hz), 4.40 (m, 1 H), 4.24 (dd, 1 H, J ) 9.7, 4.3
Hz), 3.68 (dd, 1 H, J ) 9.7, 4.9 Hz), 3.60-3.30 (m, 2 H), 1.44,
1.28 (2 s, 6 H); 13C NMR (DMSO-d6) δ 112.5, 104.1, 80.2, 78.6,
73.8, 60.7, 30.1, 26.6, 26.5. Anal. Calcd for C10H13N4O7-
SSeK: C, 26.61; H, 2.90; N, 12.41; S, 7.10. Found: C, 26.27;
H, 3.30; N, 11.93; S, 7.03.
1
1322, 1207, 1164, 1119, 1041 cm-1; H NMR (CDCl3) δ 4.66
(q, 1 H, J ) 5.0 Hz), 4.15 (dd, 1 H, J ) 10.6, 5.2 Hz), 3.80 (dt,
1 H, J ) 10.1, 5.4 Hz), 3.53 (dd, 1 H, 1 H, J ) 13.7, 2.6 Hz),
3.45 (dt, 1 H, J ) 9.3, 2.6 Hz), 3.34 (t, 1 H, J ) 10.6 Hz), 2.64
(dd, 1 H, J ) 13.7, 8.6 Hz), 2.32 (s, 3 H), 1.16 (d, 3 H, J ) 5.0
Hz); 13C NMR (CDCl3) δ 98.1, 77.6, 68.4, 30.6, 30.4, 20.0;
MSFAB m/z 363 (M + K)+, 347 (M + Na)+, 339 (M - K + 2
Na)+.
2-Aceta m ido-6-Se-cya n o-2-deoxy-3,4-O-isopr op ylid en e-
6-selen o-5-O-su lfo-a ld eh yd o-D-glu cose Dim eth yl Aceta l
P ota ssiu m Sa lt (33). Column chromatography (methanol-
chloroform 1:5) of the crude product gave 33 (63%) as a solid:
mp 183 °C dec; [R]D +15° (c 1, methanol); IR (Nujol) 3402, 2077,
1652, 1558, 1219, 1152, 1087 cm-1; 1H NMR (DMSO-d6) δ 7.61
(d, 1 H, J ) 9.6 Hz), 4.35 (m, 1 H), 4.31 (d, 1 H, J ) 7.2 Hz),
4.27 (dd, 1 H, J ) 6.7, 2.5 Hz), 4.14 (ddd, 1 H, J ) 9.6, 7.2, 2.4
Hz), 3.74 (t, 1 H, J ) 7.0 Hz), 3.49 (dd, 1 H, J ) 11.9, 5.3 Hz),
3.42 (dd, 1 H, J ) 11.9, 4.7 Hz), 3.24, 3.22 (2 s, 6 H), 1.86 (s,
3 H), 1.34, 1.31 (2 s, 6 H); 13C NMR (DMSO-d6) δ 179.5, 109.4,
105.0, 102.4, 77.5, 77.4, 75.2, 53.3, 52.0, 50.1, 31.3, 27.1, 27.0,
22.6.
Meth yl 6-S-Acetyl-2,3-d i-O-ben zyl-4-O-su lfo-6-th io-r-D-
glu cop yr a n osid e P ota ssiu m Sa lt (29). Column chroma-
tography (methanol-chloroform 1:3) of the crude product gave
29 (94%) as a solid: mp 168-169 °C; [R]D +93° (c 1, methanol);
1H NMR (DMSO-d6) δ 7.40-7.20 (m, 10 H), 4.77 (AB system,
2 H, J ) 10.9 Hz, δν ) 80.8 Hz), 4.71 (d, 1 H, J ) 3.5 Hz),
4.59 (AB system, 2 H, J ) 12.0 Hz, δν ) 13.0 Hz), 3.95 (t, 1 H,
J ) 9.3 Hz), 3.80 (dd, 1 H, J ) 13.9, 2.2 Hz), 3.58 (t, 1 H, J )
9.6 Hz), 3.48 (dt, 1 H, J ) 9.8, 2.5 Hz), 3.38 (dd, 1 H, J ) 9.6,
3.5 Hz), 3.26 (s, 3 H), 2.80 (dd, 1 H, J ) 14.1, 10.0 Hz), 2.30 (s,
3 H); 13C NMR (DMSO-d6) δ 194.7, 139.3, 138.6, 128.2, 127.7,
127.5, 127.3, 127.0, 96.8, 79.5, 78.5, 73.8, 71.7, 68.7, 54.3, 30.8,
3-O-Acet yl-6-S-cya n o-1,2-O-isop r op ylid en e-5-O-su lfo-
6-th io-â-D-a ltr ofu r a n ose P ota ssiu m Sa lt (61). Column

3956 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
chromatography (methanol-chloroform 1:3) of the crude prod-
uct gave 61 (100%) as a hygroscopic solid: mp 62 °C; [R]D -6.5°
(c 1, methanol); IR (KBr) 2161, 1742, 1252, 1163, 1069, 1019
cm-1; 1H NMR (DMSO-d6) δ 5.92 (d, 1 H, J ) 4.0 Hz), 5.29 (s,
1 H), 4.67 (dt, 1 H, J ) 10.0, 3.5 Hz), 4.59 (d, 1 H, J ) 3.8 Hz),
4.05 (d, 1 H, J ) 10.1 Hz), 3.71 (dd, 1 H, J ) 13.2, 3.9 Hz),
3.35 (dd, 1 H, J ) 13.2, 3.1 Hz), 2.05 (s, 3 H), 1.42, 1.22 (2 s,
6 H); 13C NMR (DMSO-d6) δ 169.4, 113.4, 111.4, 105.8, 83.8,
83.3, 77.2, 71.7, 36.0, 26.0, 25.4, 20.7. Anal. Calcd for
C10H14NO8S2K: C, 31.65; H, 3.72; N, 3.69. Found: C, 31.38;
H, 3.94; N, 3.41.
3-O-Be n zyl-5,6-d id e oxy-5,6-e p it h io-1,2-O-isop r op y-
lid en e-â-L-id ofu r a n ose (12d ). Column chromatography
(ether-hexane 2:1) of the crude product gave 12d (86% from
10d ) as a solid: mp 71-71 °C; [R]D -68° (c 1, chloroform); IR
1
(Nujol) 1163, 1128, 1076, 1027 cm-1; H NMR (CDCl3) δ 7.33
(m, 5 H), 5.97 (d, 1 H, J ) 3.8 Hz), 4.64 (AB system, 2 H, J )
12.1 Hz, δν ) 40.8 Hz), 4.65 (d, 1 H, J ) 3.8 Hz), 3.89 (d, 1 H,
J ) 3.3 Hz), 3.61 (dd, 1 H, J ) 8.4, 3.3 Hz), 3.21 (ddd, 1 H, J
) 8.4, 6.5, 5.5 Hz), 2.36 (dd, 1 H, J ) 6.5, 1.5 Hz), 2.08 (dd, 1
H, J ) 5.5, 1.5 Hz), 1.43, 1.31 (2 s, 6 H); 13C NMR (CDCl3) δ
137.4, 128.6, 128.2, 127.8, 111.9, 105.1, 86.2, 82.8, 82.8, 72.1,
31.5, 26.9, 26.4, 20.7; MS m/z 309 (M+ + 1), 251. Anal. Calcd
for C16H20O4S: C, 62.31; H, 6.54; S, 10.40. Found: C, 62.29;
H, 6.49; S, 10.21.
5-S-Acetyl-3-O-ben zyl-2-deoxy-4-O-su lfo-5-th io-L-er yth r o-
a ld eh yd o-p en tose Dim eth yl Aceta l P ota ssiu m Sa lt (69).
Column chromatography (methanol-chloroform 1:6) of the
crude product gave 69 (77%) as a syrup: [R]D +1° (c 5,
3,5,6-Tr id eoxy-5,6-ep ith io-1,2-O-isop r op ylid en e-â-L-id -
ofu r a n ose (12e). Column chromatography (ether-hexane
5:1) of the crude product gave 12e (91% from 10e) as a solid:
mp 124-125 °C; [R]D +8° (c 1, chloroform); IR (Nujol) 1260,
methanol); IR (neat) 1686, 1261, 1211, 1120, 1058, 985 cm-1
;
1H NMR (CDCl3) δ 7.30 (m, 5 H), 4.56 (AB system, 2 H, J )
11.5 Hz, δν ) 33.7 Hz), 4.41 (dd, 1 H, J ) 7.7, 3.7 Hz), 4.20
(m, 1 H), 3.89 (dt, 1 H, J ) 9.6, 3.2 Hz), 3.40-3.15 (m, 2 H),
3.19, 3.15 (2 s, 6 H), 2.30 (s, 3 H), 1.77 (ddd, 1 H, J ) 13.0,
8.0, 3.6 Hz), 1.62 (ddd, 1 H, J ) 13.0, 9.3, 3.5 Hz); 13C NMR
(DMSO-d6) δ 195.3, 138.8, 128.1, 127.7, 127.3, 101.8, 76.9, 75.8,
72.1, 52.5, 45.8, 35.0, 30.5, 29.3.
1
1214, 1163, 1079, 1054, 1021 cm-1; H NMR (CDCl3) δ 5.76
(d, 1 H, J ) 3.7 Hz), 4.70 (dd, 1 H, J ) 4.5, 3.8 Hz), 4.06 (ddd,
1 H, J ) 10.5, 6.1, 4.5 Hz), 2.96 (pseudo-q, 1 H, J ) 6.5 Hz),
2.42 (dd, 1 H, J ) 6.5, 1.3 Hz), 2.30 (dd, 1 H, J ) 5.5, 1.3 Hz),
2.19 (dd, 1 H, J ) 13.4, 4.5 Hz), 1.69 (ddd, 1 H, J ) 13.4, 10.5,
4.8 Hz), 1.43, 1.26 (2 s, 6 H); 13C NMR (CDCl3) δ 111.3, 105.5,
80.5, 80.1, 38.7, 36.0, 26.8, 26.2, 21.3; MS m/z 202 (M+), 187;
MS (calcd mass for C9H14O3S 202.0664) obsd m/z 202.0671.
Anal. Calcd for C9H14O3S: C, 53.44; H, 6.98; S, 15.85.
Found: C, 53.89; H, 7.04; S, 15.50.
Gen er a l P r oced u r e for th e Syn th esis of Ep isu lfid es
6, 12b-g, 18a ,b, a n d 70. (a) To a solution of the potassium
salt (1 mmol) in anhydrous methanol (15 mL) was added a
solution of NaMeO (3 mmol when the S-acetyl derivatives 4,
10a ,c-f, 16a ,b, and 69 were used and 5 mmol when the
S-cyano derivatives 5, 11a , and 17a were used) in methanol.
The reaction mixture was left at rt until TLC (methanol-
chloroform 1:5) showed complete disappearance of the starting
material. A saturated solution of ammonium chloride (15 mL)
was added, and the methanol was removed in vacuo. Water
(15 mL) was added, and the resulting solution was extracted
with ethyl acetate (3 × 25 mL). The organic layers were
collected, dried, and evaporated.
3-Azido-3,5,6-tr ideoxy-5,6-epith io-1,2-O-isopr opyliden e-
â-L-ta lofu r a n ose (12f). Column chromatography (ether) of
the crude product gave 12f (83% from 10f) as a solid: mp 54
°C; [R]D +284° (c 1, chloroform); IR (BrK) 2110, 1260, 1218,
1
1167, 1112, 1078, 1046, 1018 cm-1; H NMR (CDCl3) 5.77 (d,
1 H, J ) 3.7 Hz), 4.73 (pseudo-t, 1 H, J ) 4.2 Hz), 3.38 (dd, 1
H, J ) 9.3, 6.4 Hz), 3.35 (dd, 1 H, J ) 9.3, 4.6 Hz), 3.02 (t, 1
H, J ) 6.5 Hz), 2.53 (dd, 1 H, J ) 6.5, 1.4 Hz), 2.45 (dd, 1 H,
J ) 5.4, 1.4 Hz), 1.52, 1.33 (2 s, 6 H); 13C NMR (CDCl3) δ 113.4,
104.0, 80.2, 65.3, 34.2, 26.4, 26.2, 21.3; MS m/z 228 (M+ - CH3),
186. Anal. Calcd for C9H13N3O3S: C, 44.43; H, 5.39; N, 17.27;
S, 13.18. Found: C, 44.45; H, 5.40; N, 17.00; S, 13.041.
2-Aceta m id o-2,5,6-tr id eoxy-5,6-ep ith io-3,4-O-isop r op y-
lid en e-a ld eh yd o-L-id ose Dim eth yl Aceta l (18a ). Column
chromatography (ethyl acetate) of the crude product gave 18a
(70% from 16a and 63% from 17a ) as a solid: mp 135-36 °C;
[R]D +55° (c 1, chloroform); IR (Nujol) 3283, 1645, 1541, 1084
(2R)-1-(Ben zyloxy)-2,3-epith iopr opan e (6). Column chro-
matography (ether) of the crude product gave 6 (95% from 4
and 71% from 5) as a syrup: [R]D +11° (c 10, chloroform); IR
1
(neat) 1451, 1368, 1096, 1047; H NMR (CDCl3) δ 7.38 (m, 5
H), 4.60 (bs, 2 H), 3.70 (ddd, 1 H, J ) 10.6, 5.7, 0.7 Hz), 3.51
(dd, 2 H, J ) 10.6, 6.7 Hz), 3.12 (m, 1 H), 2.52 (bd, 1 H, J )
6.2 Hz), 2.22 (dd, 1 H, J ) 5.4, 1.2 Hz); 13C NMR (CDCl3) 137.9,
128.4, 127.7, 74.6, 73.0, 32.1, 23.7; MS m/z 181 (M+ + 1), 147,
91; MS (CI+) (calcd mass for C10H12OS + H 181.0687) obsd
m/z 181.0588.
1
cm-1; H NMR (CDCl3) δ 5.78 (d, 1 H, J ) 9.7 Hz), 4.43 (d, 1
H, J ) 6.9 Hz), 4.28 (ddd, 1 H, J ) 9.8, 6.9, 1.3 Hz), 4.18 (dd,
1 H, J ) 8.5, 1.3 Hz), 3.44, 3.34 (2 s, 6 H), 3.27 (pseudo-t, 1 H,
J ) 8.0 Hz), 2.97 (ddd, 1 H, J ) 7.6, 6.4, 5.3 Hz), 2.53 (dd, 1
H, J ) 5.3, 1.4 Hz), 2.49 (dd, 1 H, J ) 6.4, 1.4 Hz), 2.03 (s, 3
H), 1.45, 1.39 (2 s, 6 H); 13C NMR (CDCl3) δ 169.9, 109.4, 102.9,
81.8, 78.6, 55.5, 52.5, 48.6, 34.0, 27.1, 27.0, 23.3, 21.3; MS
(calcd mass for C13H24NO5S 306.1365) obsd m/z 306.1375.
4,5-Dideoxy-4,5-epith io-2,3-O-isopr opyliden e-a ldeh ydo-
L-xylose Dim eth yl Aceta l (18b). Column chromatography
(ether-hexane 2:1) of the crude product gave 18b (67% from
16b) as a syrup: [R]D +32° (c 1, chloroform); IR (neat) 1213,
1152, 1081 cm-1; 1H NMR (CDCl3) δ 4.38 (d, 1 H, J ) 5.4 Hz),
4.04 (dd, 1 H, J ) 7.0, 5.4 Hz), 3.78 (t, 1 H, J ) 6.7 Hz), 3.48,
3.46 (2 s, 6 H), 3.05 (dt, 1 H, J ) 6.4, 5.3 Hz), 2.52 (dd, 1 H, J
) 6.3, 1.3 Hz), 2.39 (dd, 1 H, J ) 5.3, 1.3 Hz), 1.46, 1.43 (2 s,
6 H); 13C NMR (CDCl3) δ 110.3, 104.3, 81.1, 80.1, 56.1, 54.4,
34.4, 27.3, 27.1, 22.3; MS (calcd mass for C10H18O4S + H
235.1004) obsd m/z 235.1007.
5,6-Did eoxy-5,6-ep it h io-1,2-O-isop r op ylid en e-â-L-id -
ofu r a n ose (12b). Column chromatography (ether) of the
crude product gave 12b (90% from 10a and 70% from 11a ) as
a solid: mp 168-170 °C (lit.135 mp 164-165 °C); [R]D -5° (c 1,
chloroform) (lit.134 [R]D -16°); IR (KBr) 3418, 1221, 1162, 1092,
1
1066, 1002 cm-1; H NMR (CDCl3) 5.94 (d, 1 H, J ) 3.7 Hz),
4.53 (d, 1 H, J ) 3.7 Hz), 4.20 (dd, 1 H, J ) 6.1, 2.7 Hz), 3.87
(dd, 1 H, J ) 7.3, 2.7 Hz), 3.15 (ddd, 1 H, J ) 7.1, 6.8, 5.5 Hz),
2.50 (dd, 1 H, J ) 6.6, 1.4 Hz), 2.33 (dd, 1 H, J ) 5.5, 1.4 Hz),
2.05 (d, 1 H, J ) 6.1 Hz), 1.46, 1.30 (2 s, 6 H); 13C NMR (CDCl3)
δ 112.1, 104.6, 85.6, 83.6, 31.1, 26.8, 26.3, 20.4; MS m/z 218
(M+), 203 (M+ - CH3); MS (calcd mass for C9H14O4S 218.0613)
obsd m/z 218.0621. Anal. Calcd for C9H14O4S: C, 59.52; H,
6.46, S, 14.69. Found: C, 49.06; H, 6.30; S, 15.00.
5,6-Did e oxy-5,6-e p it h io-3-O-m e t h yl-1,2-O-isop r op y-
lid en e-â-L-id ofu r a n ose (12c). Column chromatography
(ether-hexane 2:1) of the crude product gave 12c (79% from
10c) as a solid: mp 89-90 °C; [R]D -47° (c 1, chloroform); IR
3-O-Ben zyl-2,4,5-tr ideoxy-4,5-epith io-a ldeh ydo-D-th r eo-
p en tose Dim eth yl Aceta l (70). Column chromatography
(ether-hexane 3:1) of the crude product gave 70 (83% from
69) as a syrup: [R]D +42° (c 1, chloroform); IR (neat) 1232,
1
(KBr) 1185, 1163, 1120, 1081, 1017 cm-1; H NMR (CDCl3) δ
5.93 (d, 1 H, J ) 3.9 Hz), 4.61 (d, 1 H, J ) 3.8 Hz), 3.68 (d, 1
H, J ) 3.3 Hz), 3.62 (dd, 1 H, J ) 8.4, 3.3 Hz), 3.46 (s, 3 H),
3.15 (ddd, 1 H, J ) 8.4, 6.5, 4.4 Hz), 2.49 (dd, 1 H, J ) 6.5, 1.4
Hz), 2.22 (dd, 1 H, J ) 5.4, 1.4 Hz), 1.44, 1.31 (2 s, 6 H); 13C
NMR (CDCl3) δ 111.8 (CMe2), 104.9, 86.1, 85.4, 82.0, 58.2, 31.3,
26.9, 26.3, 20.9; MS m/z 233 (M+ + 1). Anal. Calcd for
C10H16O4S: C, 51.71; H, 6.94, S, 13.80. Found: C, 51.77; H,
6.95; S, 12.97.
1182, 1124, 1098, 1073 cm-1 1H NMR (CDCl3) δ 7.36-7.30
;
(m, 5 H), 4.72 (AB system, 2 H, J ) 11.6 Hz, δν ) 35.5 Hz),
4.56 (dd, 1 H, J ) 7.3, 4.2 Hz), 3.30, 3.26 (2 s, 6 H), 3.28-3.22
(m, 1 H), 2.97 (ddd, 1 H, J ) 7.7, 6.5, 5.6 Hz), 2.43(dd, 1 H, J
) 6.5, 1.4 Hz), 2.13 (dd, 1 H, J ) 5.6, 1.4 Hz), 2.01 (ddd, 1 H,
J ) 14.1, 8.6, 4.2 Hz), 1.91 (ddd, 1 H, J ) 14.1, 7.4, 4.1 Hz);
13C NMR (CDCl3) δ 138.4, 128.3, 127.9, 127.6, 101.8, 80.1, 71.7,
53.4, 52.7, 38.6, 36.5, 20.0; MS m/z 237 (M+ + 1 - CH4O), 205,
179, 147.
(135) Creighton, A. M.; Owen, L. N. J . Chem. Soc. 1960, 1024.

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3957
Syn th esis of 3,4-Did eoxy-3,4-ep ith io-1,2:5,6-d i-O-iso-
p r op ylid en e-D-id itol (20). To a solution of 19 (1mmol) in
methanol (60 mL) was added NaS2‚9H2O (0.27 g). The reaction
mixture was heated under reflux for 30 min. After cooling
and evaporation under vacuum, the crude was dissolved in
EtOAc (75 mL) and washed with water (25 mL). The organic
layer was dried, filtered, and evaporated. The residue was
purified by column chromatography (ether-hexane 4:1) to give
20 (110 mg, 42%) as a solid: mp 45-47 °C; [R]D -15° (c 2,
MS (calcd mass for C9H15O4 + H 187.0970) obsd m/z 187.0976.
Anal. Calcd for C9H14O4: C, 58.05; H, 7.58. Found: C, 58.04;
H, 7.70.
5,6-Did eoxy-1,2-O-isop r op ylid en e-3-O-m eth yl-r-D-xylo-
h ex-5-en ofu r a n ose (32c). Column chromatography (ether-
hexane 3:1) of the crude product gave 32c (50%) as a syrup:
[R]D -70° (c 1, chloroform); IR (Nujol) 1645, 1256, 1217, 1195,
1165, 1116, 1080 cm-1 1H NMR (CDCl3) δ 5.96-5.87 (m, 2
;
H), 5.41 (bd, 1 H, J ) 17.3 Hz), 5.28 (bd, 1 H, J ) 10.5 Hz),
4.58 (m, 2 H), 3.64 (bs, 1 H), 3.35 (s, 3 H), 1.49, 1.31 (2 s, 6 H);
13C NMR (CDCl3) δ 132.0, 118.6, 111.4, 104.7, 85.6, 82.0, 81.2,
58.1, 26.7, 26.1; MS m/z 201 (M+ + 1), 185 (M+), 143; MS (calcd
mass for C10H16O4 + H 201.1127) obsd m/z 201.1111.
chloroform); IR (KBr) 1370, 1253, 1209, 1152, 1050, 790 cm-1
;
1H NMR (CDCl3) δ 4.17 (dd, 1 H, J ) 8.6, 4.6 Hz), 4.15 (dd, 1
H, J ) 8.6, 4.1 Hz), 4.04-3.95 (m, 2 H), 3.88-3.80 (m, 2 H),
3.06 (dd, 1 H, J ) 7.6, 4.3 Hz), 2.98 (dd, 1 H, J ) 8.2, 4.3 Hz),
1.45, 1.40, 1.36, 1.31 (4s, 12 H); 13C NMR (CDCl3) δ 110.3,
109.9, 75.2, 74., 68.6, 66.6, 57.5, 56.0, 26.9, 26.7, 25.6, 25.3;
MS m/z 245 (M+ - CH3), 229. Anal. Calcd for C12H20O4S: C,
55.36; H, 7.35. Found: C, 55.56; H, 8.00.
Tr ea t m en t of t h e Cyclic Su lfa t es 9a ,d w it h Sod iu m
Su lfid e. To a solution of the cyclic sulfate 9a ,d (1 mmol) in
acetone (15 mL) was added a solution of Na2S‚9H2O (0.24 g, 1
mmol) in acetone-water (15:2 mL). The reaction mixture was
left at rt for 2 h until TLC (methanol-chloroform 1:3) showed
complete disappearance of the starting material. The reaction
mixture was evaporated under vacuum and coevaporated with
toluene (3 × 10 mL), giving a crude product that was purified
by column chromatography (methanol-chloroform 1:2).
3-O-Ben zyl-5,6-d id eoxy-1,2-O-isop r op ylid en e-r-D-xylo-
h ex-5-en ofu r a n ose (32d ). Column chromatography (ether-
hexane 1:2) of the crude product gave 32d (94.0%) as a syrup:
[R]D -79° (c 1, chloroform) [lit.136 [R]D -56.4° (c 3.22, chloro-
form)]; IR (neat) 1645, 1494, 1253, 1225, 1165, 1066, 1008
1
cm-1; H NMR (CDCl3) δ 7.30 (m, 5 H), 6.02 (ddd, 1 H, J )
17.5, 10.4, 7.1 Hz), 5.96 (d, 1 H, J ) 3.8 Hz), 5.43 (bd, 1 H, J
) 17.3 Hz), 5.31 (bd, 1 H, J ) 10.5 Hz), 4.63 (m, 1 H), 4.62 (d,
1 H, J ) 3.3 Hz), 4.59 (AB system, 2 H, J ) 12.2 Hz, δν ) 21.0
Hz), 3.88 (d, 1 H, J ) 3.1 Hz), 1.50, 1.32 (2 s, 6 H); 13C NMR
(CDCl3) δ 137.6, 128.5, 127.9, 127.6, 132.3, 119.0, 111.5, 104.9,
83.5, 83.0, 81.6, 72.1, 26.9, 26.3; MS m/z 277 (M+ + 1), 219.
3,5,6-Tr id eoxy-1,2-O-isop r op ylid en e-r-D-er yth r o-h ex-5-
en ofu r a n ose (32e). Column chromatography (ether-hexane
2:1) of the crude product gave 32e (67%) as a syrup: [R]D -2.5°
(c 1, chloroform); IR (neat) 1457, 1215, 1162, 1117, 1076, 1023
Bis[1,2-O-isopr opyliden e-5-O-su lfo-r-D-glu cofu r an osid-
6-yl] Su lfid e Disod iu m Sa lt (21). Column chromatography
of the crude product gave 21 (0.290 g, 90%) isolated as a
solid: mp 170-172 °C; [R]D -29° (c 1, methanol); IR (KBr)
1
cm-1; H NMR (CDCl3) δ 5.80 (ddd, 1 H, J ) 17.2, 10.4, 6.6
Hz), 5.80 (d, 1 H, J ) 3.1 Hz), 5.31 (dt, 1 H, J ) 17.2, 1.2 Hz),
5.16 (dt, 1 H, J ) 10.4, 1.2 Hz), 4.70 (t, 1 H, J ) 4.3 Hz), 4.60
(m, 1 H), 2.14 (dd, 1 H, J ) 13.4, 4.4 Hz), 1.57 (ddd, 1 H, J )
13.4, 10.5, 4.7 Hz), 1.49, 1.29 (2 s, 6 H); MS m/z 171 (M+ + 1),
113.
1
3444, 1221, 1074, 956, 912 cm-1; H NMR (DMSO-d6) δ 5.82
(d, 2 H, J ) 3.6 Hz), 5.12 (d, 2 H, J ) 2.6 Hz), 4.42 (d, 2 H, J
) 3.6 Hz), 4.32 (dt, 2 H, J ) 9.7, 2.9 Hz), 4.22 (dd, 2 H, J )
9.6, 2.1 Hz), 4.05 (t, 2 H, J ) 2.4 Hz), 3.04 (dd, 2 H, J ) 14.4,
3.2 Hz), 2.89 (dd, 2 H, J ) 14.4, 2.6 Hz), 1.38, 1.23 (2 s, 12 H);
13C NMR (DMSO-d6) δ 110.8, 104.6, 84.1, 79.3, 73.7, 71.9, 36.7,
26.7, 26.3; MS (FAB) m/z 665 (M+ + Na). Anal. Calcd for
3-Azid o-3,5,6-t r id eoxy-1,2-O-isop r op ylid en e-r-D-r ibo-
h ex-5-en ofu r a n ose (32f). Column chromatography (ether-
hexane 1:3) of the crude product gave 32f (60%) as a solid:
mp 55-57 °C; [R]D +99° (c 1, chloroform); IR (KBr) 2108, 2160,
C
18H28O16S3Na2‚3H2O: C, 31.03; H, 4.92. Found: C, 31.29;
H, 4.62.
Bis[1,2-O-isop r op ylid en e-3-O-ben zyl-5-O-su lfo-r-D-glu -
1
1069 cm-1; H NMR (CDCl3) δ 5.85 (ddd, 1 H, J ) 17.2, 10.3,
6.8 Hz), 5.82 (d, 1 H, J ) 3.8 Hz), 5.51 (d, 1 H, J ) 17.2 Hz),
5.36 (d, 1 H, J ) 10.4 Hz), 4.71 (t, 1 H, J ) 4.2 Hz), 4.49 (dd,
1 H, J ) 9.6, 6.9 Hz), 3.18 (dd, 1 H, J ) 9.6, 4.6 Hz), 1.59, 1.35
(2 s, 6 H); 13C NMR (CDCl3) 133.7, 120.2, 113.1, 104.0, 79.9,
78.6, 64.9, 26.4, 26.3; MS m/z 292 (M+ - CH3), 249. Anal.
Calcd for C9H13N3O3: C, 51.18; H, 6.20; N, 19.89. Found: C,
51.36; H, 6.46; N, 19.54.
cofu r a n osid -6-yl] Su lfid e Disod iu m Sa lt (22). Column
chromatography of the crude product gave 22 (0.514 g, 62.5%)
isolated as a solid: mp 144 °C dec; [R]D -14° (c 1, methanol);
IR (KBr) 1219, 1164, 1078, 1035, 995, 958 cm-1 1H NMR
;
(DMSO-d6) δ 7.45-7.30 (m, 10 H), 5.76 (d, 2 H, J ) 3.8 Hz),
4.67-4.51 (m, 6 H), 4.60 (d, 2 H, J ) 3.9 Hz), 4.30 (dd, 2 H, J
) 7.9, 2.7 Hz), 3.89 (d, 2 H, J ) 2.5 Hz), 3.20 (dd, 2 H, J ) 4.1,
3.3 Hz), 2.83 (dd, 2 H, J ) 14.1, 3.5 Hz), 1.40, 1.24 (2 s, 12 H);
13C NMR (DMSO-d6) δ 138.3, 128.3, 128.0, 127.4, 110.9, 104.3,
81.8, 80.9, 79.2, 72.4, 71.5, 35.9, 26.9, 26.5. Anal. Calcd for
2,5,6-Tr id eoxy-2-a ceta m id o-3,4-O-isop r op ylid en e-a ld e-
h yd o-D-xylo-h ex-5-en e Dim eth yl Aceta l (34). Column chro-
matography (ethyl acetate) of the crude product gave 34 (59%)
as a solid: mp 109-110 °C; [R]D +14°, [R]436 +24.5° (c 1,
chloroform); IR (Nujol) 3277, 1647, 1558, 1312, 1292, 1244,
1151, 1076 cm-1; 1H NMR (CDCl3) δ 6.00 (d, 1 H, J ) 9.6 Hz),
5.82 (ddd, 1 H, J ) 17.2, 10.3, 7.0 Hz), 5.45 (ddd, 1 H, J )
17.2, 1.4, 0.8 Hz), 5.28 (ddd, 1 H, J ) 10.3, 1.4, 0.8 Hz), 4.39
(d, 1 H, J ) 6.5 Hz), 4.24 (ddd, 1 H, J ) 9.8, 6.6, 1.2 Hz), 4.05
(bt, 1 H, J ) 8.0 Hz), 3.95 (dd, 1 H, J ) 8.7, 1.2 Hz), 3.40, 3.32
(2 s, 6 H), 2.06 (s, 3 H), 1.43, 1.41 (2 s, 6 H); 13C NMR (CDCl3)
δ 169.7, 134.2, 119.6, 109.2, 103.0, 79.2, 78.5, 55.1, 52.6, 47.6,
27.0, 26.8, 23.2; MS (calcd mass for C13H23NO5 + H 274.1654)
obsd m/z 274.1665. Anal. Calcd for C13H23NO5: C, 57.13; H,
8.48; N, 5.12. Found: C, 57.28; H, 8.22; N, 5.40.
C
32H40O16S3Na2: C, 46.71; H, 4.90. Found: C, 46.79; H, 5.26.
Gen er a l P r oced u r e for th e Syn th esis of Olefin s 32b-
f, 34, a n d 37. Cyclic sulfate 9a ,c-f, 15a , or 36 (1 mmol) was
treated with potassium selenium cyanate following the general
procedure described above (except for 36 where 2.2 mmol of
KSeCN was used). After evaporation of the acetone, the crude
product was disolved in methanol (15 mL), and NaBH4 (5
mmol) was then added portionwise under stirring. The
reaction mixture was left at rt until TLC (methanol-
chloroform 1:5) showed complete disappearance of the sele-
nium cyanate salt (4-12 h). Methanol was removed in vacuo,
and then water (25 mL) was added. The aqueous solution was
extracted with AcOEt (3 × 25 mL), and the organic layers were
collected, dried, and evaporated.
(3R,4R)-3,4-Bis(ben zyloxy)-1,5-h exa d ien e (37). Column
chromatography (ether-hexane 1:1) of the crude product gave
37 (45%) as a liquid: [R]D -10°, [R]436 -15.6° (c 1.5, chloro-
1
form); IR (neat) 3064, 3029, 1494, 1092, 1070, 1028 cm-1; H
5,6-Did eoxy-1,2-O-isop r op ylid en e-r-D-xylo-h ex-5-en o-
fu r a n ose (32b). Column chromatography (ether-hexane 2:1)
of the crude product gave 32b (50%) as a solid: mp 62-64 °C
(lit.32 mp 61-65 °C); [R]D -36° (c 1, chloroform) [lit.32 [R]D -60°
(c 2, chloroform)]; IR (Nujol) 3422, 1292, 1246, 1125, 1162,
NMR (CDCl3) δ 7.43-7.30 (m, 10 H), 5.94-5.83 (m, 2 H), 5.34
(d, 2 H, J ) 16.2 Hz), 5.32 (dd, 2 H, J ) 6.0, 1.0 Hz), 4.62 (AB
system, 4 H, J ) 12.2 Hz, δν ) 35.7 Hz), 3.94 (m, 2 H); 13C
NMR (CDCl3) δ, 138.7, 128.4, 127.8, 127.5, 135.3, 118.6, 82.5,
70.8; MS (calcd mass for C20H22O2 + H 295.1698) obsd m/z
295.1687.
1
1114, 1085 cm-1; H NMR (CDCl3) 5.90 (d, 1 H, J ) 4.0 Hz),
5.85 (ddd, 1 H, J ) 17.0, 11.0, 5.0 Hz), 5.47 (dt, 1 H, J ) 17.0,
2.0 Hz), 5.35 (dt, 1 H, J ) 11.0, 2.0 Hz), 4.66 (m, 1 H), 4.51 (d,
1 H, J ) 4.0 Hz), 4.04 (d, 1 H, J ) 2.0 Hz), 2.20 (s, 1 H), 1.46,
1.27 (2 s, 6 H); 13C NMR (CDCl3) δ 131.4, 119.6, 111.7, 104.6,
85.0, 85.1, 75.8, 26.7, 26.2; MS m/z 187 (M+ + 1), 171, 169;
Gen er a l P r oced u r e for th e Op en in g of Ep isu lfid es
w ith Sod iu m Aceta te. A mixture of episulfide 6, 12a ,c,d ,
(136) English, J .; Levy, M. F. J . Am. Chem. Soc. 1956, 78, 2846.

3958 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
18a ,b, or 70 (1 mmol) and anhydrous sodium acetate (1.5 g)
in acetic anhydride (7 mL) and acetic acid (1.5 mL) was heated
at 140 °C under an argon atmosphere until TLC showed
complete disappearance of the starting material. The reaction
was cooled and then was poured into ice-water, and the
aqueous solution was extracted with chloroform (100 mL). The
chloroform solution was successively washed with a saturated
aqueous solution of sodium bicarbonate (3 × 100 mL) and
water (50 mL), dried, and evaporated.
3.63 (ddd, 0.4 H, J ) 6.4, 5.5 Hz), 3.29, 3.27 (2 s, 3 H), 2.40-
2.27 (m, 2 H), 2.01, 2.00 (2s, 3 H); 13C NMR (CDCl3) δ 170.7,
137.8, 128.3, 127.8, 127.7, 88.2, 86.6, 80.6, 80.0, 72.1, 71.2, 64.5,
57.0, 56.6, 48.2, 45.9, 40.8, 40.0, 20.9, 20.8; MS m/z 297 (M+
+
1), 295, 237.
Gen er a l P r oced u r e for th e Syn th esis of th e Th iol
Der iva tives 40b-d , 43a ,b, a n d 72. A mixture of the
potassium salts 11a ,c,d and 17a (1 mmol) or the episulfide
12b,d , 18a ,b, or 70 (1 mmol) and lithium aluminum hydride
(6 mmol for 11a ,c,d and 17a and 4 mmol for 12b,d , 18a ,b,
and 70) in dry THF (20 mL) was stirred at rt until TLC showed
complete disappearance of the starting material. After cooling,
ethyl acetate (25 mL) was added. The solid was filtered
through Celite, and the solution was evaporated. The residue
was dissolved in ethyl acetate (100 mL) and washed with water
(30 mL). The organic layer was dried, concentrated, and
evaporated.
6-Deoxy-1,2-O-isop r op ylid en e-5-t h io-â-L-id ofu r a n ose
(40b). Column chromatography (ether) of the crude product
gave 40b (84% from 11a and 98% from 12b) as a solid: mp
91-92 °C (from ether-hexane) (lit.134 mp 93-94 °C); [R]D -20°
(c 1, chloroform) (lit.134 [R]D -24°); IR (KBr) 3467, 1217, 1165,
1071, 1013 cm-1; 1H NMR (CDCl3) δ 5.91 (d, 1 H, J ) 3.8 Hz),
4.50 (d, 1 H, J ) 3.8 Hz), 4.15 (dd, 1 H, J ) 6.4, 2.7 Hz), 3.94
(dd, 1 H, J ) 8.4, 2.7 Hz), 3.28 (ddq, 1 H, J ) 8.4, 6.9, 5.4 Hz),
2.27 (dd, 1 H, J ) 6.5 Hz), 2.12 (d, 1 H, J ) 5.4 Hz), 1.49, 1.30
(2 s, 6 H), 1.34 (d, 3 H, J ) 6.9 Hz); 13C NMR (CDCl3) δ 111.9,
104.3, 85.8, 85.4, 75.0, 33.7, 26.8, 26.3, 20.7; MS m/z 220 (M+),
205, 159. Anal. Calcd for C9H16O4S: C, 49.07; H, 7.32, S,
14.55. Found: C, 49.18; H, 7.12; S, 14.16.
6-Deoxy-1,2-O-isop r op ylid en e-3-O-m et h yl-5-t h io-â-L-
id ofu r a n ose (40c). Column chromatography (ether-hexane
1:1) of the crude product gave 40c (65% from 11c) as a syrup:
[R]D -68° (c 1, chloroform); IR (neat) 2580, 1256, 1216, 1190,
1167, 1118, 1079, 1023 cm-1; 1H NMR (CDCl3) δ 5.88 (d, 1 H,
J ) 3.9 Hz), 4.61 (d, 1 H, J ) 3.9 Hz), 3.94 (dd, 1 H, J ) 9.7,
3.1 Hz), 3.64 (d, 1 H, J ) 3.1 Hz), 3.40 (s, 3 H), 3.31 (ddq, 1 H,
J ) 9.7, 6.9, 5.0 Hz), 2.11 (dd, 1 H, J ) 5.0 Hz), 1.51, 1.33 (2
s, 6 H), 1.25 (d, 3 H, J ) 6.9 Hz); 13C NMR (CDCl3) δ 111.6,
104.6, 86.3, 83.4, 81.6, 57.6, 33.4, 26.8, 26.2, 19.3; MS m/z 234
(M+), 173; MS (calcd mass for C10H18O4S + H 235.1004) obsd
m/z 235.0993.
(2R)-1-Acetoxy-2-(acetylth io)-3-(ben zyloxy)pr opan e (38).
Column chromatography (ether-hexane 1:3) of the crude
product gave 38 (37%) as a syrup: [R]D +1.5° (c 4.5, chloro-
1
form); IR (neat) 1742, 1692, 1235, 1108, 1030, 954 cm-1; H
NMR (CDCl3) δ 7.38-7.30 (m, 5 H), 4.54 (bs, 2 H), 4.30 (dd, 1
H, J ) 11.2, 6.3 Hz), 4.25 (dd, 1 H, J ) 11.2, 5.5 Hz), 3.12
(ddt, 1 H, J ) 6.3, 5.5, 4.6 Hz), 3.66 (dd, 1 H, J ) 9.9, 4.6 Hz),
3.57 (dd, 1 H, J ) 9.9, 6.3 Hz), 2.34, 2.01 (2 s, 6 H); 13C NMR
(CDCl3) δ 137.8, 128.5, 127.8, 127.7, 73.2, 68.8, 63.3, 42.5, 30.7,
20.8; MS (calcd mass for C14H18O4S + H 283.1004) obsd m/z
283.0995.
3,6-Di-O-a cetyl-5-S-a cetyl-1,2-O-isop r op ylid en e-5-th io-
â-L-id ofu r a n ose (39a ). Column chromatography (ether-
hexane 1:2) of the crude product gave 39a (61%) as a solid:
mp 60-61 °C (lit.83 mp 69-70 °C); [R]D +9.5° (c 1, chloroform)
[lit.83 [R]D +10° (c 0.6, chloroform)]; IR (KBr) 1736, 1688, 1431,
1375, 1214, 1164, 1089 cm-1; 1H NMR (CDCl3) δ 5.79 (d, 1 H,
J ) 3.8 Hz), 5.13 (d, 1 H, J ) 3.0 Hz), 4.44 (d, 1 H, J ) 3.8
Hz), 4.29 (dd, 1 H, J ) 8.4, 2.9 Hz), 4.16 (dd, 1 H, J ) 13.2,
8.2 Hz), 4.10-3.99 (m, 2 H), 2.28, 2.05, 1.94 (3 s, 9 H), 1.42,
1.22 (2 s, 6 H); 13C NMR (CDCl3) δ 193.7, 170.2, 169.6, 112.1,
104.0, 83.5, 77.2, 76.2, 63.8, 41.4, 30.5, 26.5, 26.1, 20.8, 20.5
MS m/z 363 (M+ + 1), 306, 305, 245. Anal. Calcd for
C15H22O8S: C, 49.72; H, 6.12, S, 8.85. Found: C, 49.90; H,
6.34; S, 8.75.
6-O-Acetyl-5-S-acetyl-3-O-m eth yl-1,2-O-isopr opyliden e-
5-t h io-â-L-id ofu r a n ose (39c). Column chromatography
(ether-hexane 3:1) of the crude product gave 39c (92%) as a
syrup: [R]D -31° (c 4.3, chloroform); IR (neat) 1743, 1692,
1
1232, 1165, 1114, 1077, 1023 cm-1; H NMR (CDCl3) δ 5.86
(d, 1 H, J ) 3.9 Hz), 4.57 (d, 1 H, J ) 3.9 Hz), 4.31-4.13 (m,
4 H), 3.68 (d, 1 H, J ) 2.8 Hz), 3.39 (s, 3 H), 2.32, 2.04 (2 s, 6
H), 1.46, 1.29 (2 s, 6 H); 13C NMR (CDCl3) δ 194.1, 170.6, 111.7,
104.7, 84.0, 81.3, 78.6, 64.2, 57.5, 42.0, 30.6, 26.7, 26.2, 20.8;
MS m/z 335 (M+ + 1), 319, 275, 217; MS (calcd mass for
C14H22O7S 335.1164) obsd m/z 335.1151.
3-O-Ben zyl-6-d eoxy-1,2-O-isop r op ylid en e-5-th io-â-L-id -
ofu r a n ose (40d ). Column chromatography (ether-hexane
1:2) of the crude product gave 40d (59% from 11d and 66%
from 12d ) as a solid: mp 54-56 °C; [R]D -66° (c 1, chloroform);
6-O-Acetyl-5-S-a cetyl-3-O-ben zyl-1,2-O-isop r op ylid en e-
5-t h io-â-L-id ofu r a n ose (39d ). Column chromatography
(ether-hexane 1:1) of the crude product gave 39d (95%) as a
syrup: [R]D -36° (c 1, chloroform); IR (neat) 1742, 1696, 1227,
1
IR (neat) 2588, 1256, 1219, 1168, 1080, 1027 cm-1; H NMR
(CDCl3) δ 7.40-7.25 (m, 5 H), 5.91 (d, 1 H, J ) 3.8 Hz), 4.56
(AB system, 2 H, J ) 11.6 Hz, δν ) 45.1 Hz), 4.66 (d, 1 H, J
) 3.8 Hz), 3.94 (dd, 1 H, J ) 9.7, 3.2 Hz), 3.87 (d, 1 H, J ) 3.2
Hz), 3.39 (ddq, 1 H, J ) 9.6, 6.9, 4.2 Hz), 2.11 (d, 1 H, J ) 4.2
Hz), 1.50, 1.32 (2 s, 6 H), 1.13 (d, 3 H, J ) 6.9 Hz); 13C NMR
(CDCl3) δ 137.0, 128.5, 128.1, 127.9, 111.7, 104.6, 86.3, 82.1,
81.0, 71.8, 33.3, 26.8, 26.3, 19.1. Anal. Calcd for C16H22O4S:
C, 61.91; H, 7.14. Found: C, 62.12; H, 7.14.
1164, 1075, 1029 cm-1 1H NMR (CDCl3) δ 7.35-7.30 (m, 5
;
H), 5.92 (d, 1 H, J ) 3.8 Hz), 4.63 (d, 1 H, J ) 3.8 Hz), 4.60
(AB system, 2 H, J ) 11.7 Hz, δν ) 32.5 Hz), 4.34-4.14 (m, 4
H), 3.95 (d, 1 H, J ) 3.1 Hz), 2.31, 2.02, (2 s, 6 H), 1.48, 1.31
(2 s, 6 H); 13C NMR (CDCl3) δ 194.2, 170.5, 136.8, 128.6, 127.9,
127.5, 111.8, 104.8, 81.9, 78.5, 71.9, 64.0, 42.1, 30.5, 26.8, 26.3,
20.7; MS m/z 411 (M+ + 1), 353, 351, 293; MS (calcd mass for
C20H26O7S + H 411.1477) obsd m/z 411.1471.
2-Aceta m id o-2,6-d id eoxy-3,4-O-isop r op ylid en e-5-th io-
a ld eh yd o-L-id ose Dim eth yl Aceta l (43a ). Column chroma-
tography (ether) of the crude product gave 43a (31% from 17a
and 80% from 18a ) as a solid: mp 95-96 °C; [R]D +37° (c 1,
chloroform); IR (KBr) 3275, 3082, 2582, 1647, 1559, 1312, 1256,
2-Acet a m id o-6-O-a cet yl-5-S-a cet yl-2-d eoxy-3,4-O-iso-
p r op ylid en e-5-t h io-a ld eh yd o-L-id ose Dim et h yl Acet a l
(42a ). Column chromatography (ethyl acetate-hexane 2:1) of
the crude product gave 34 (15%) first. Eluted second was 42a
(60%) as a syrup: [R]D +21° (c 0.9, chloroform); IR (neat) 3258,
1
1212, 1109, 1068 cm-1; H NMR (CDCl3) δ 5.91 (d, 1 H, J )
9.6 Hz), 4.40 (d, 1 H, J ) 6.4 Hz), 4.30-4.20 (m, 2 H), 3.62
(dd, 1 H, J ) 8.1, 4.9 Hz), 3.42, 3.33 (2 s, 6 H), 3.04 (ddq, 1 H,
J ) 7.3, 7.1, 4.9 Hz), 2.05 (s, 3 H), 1.83 (d, 1 H, J ) 7.3 Hz),
1.43, 1.41 (2 s, 6 H), 1.39 (d, 1 H, J ) 7.0 Hz); 13C NMR (CDCl3)
δ 169.8, 109.2, 103.2, 81.9, 77.2, 55.4, 52.8, 49.4, 36.7, 27.3,
27.2, 23.3, 22.1; MS (calcd mass for C13H25NO5S + H 308.1531)
obsd m/z 308.1552.
1
1746, 1689, 1637, 1559, 1231, 1099 cm-1; H NMR (CDCl3) δ
5.87 (d, 1 H, J ) 9.4 Hz), 4.31 (d, 1 H, J ) 5.6 Hz), 4.27-3.95
(m, 6 H), 3.34, 3.31 (2 s, 6 H), 2.34, 2.03, 1.99 (3 s, 9 H), 1.36,
1.31 (2 s, 6 H); 13C NMR (CDCl3) δ 194.0, 170.5, 169.8, 109.6,
103.4, 76.4, 76.0, 64.3, 55.2, 53.6, 48.9, 43.5, 30.6, 27.0, 23.2,
20.7; MS (calcd mass for C17H29NO8S + H 408.1692) obsd m/z
408.1660.
5-Deoxy-2,3-O-isop r op ylid en e-4-t h io-a ld eh yd o-L-a r a -
bin o-p en tose Dim eth yl Aceta l (43b). Column chromatog-
raphy (ether) of the crude product gave 43b (93% from 18b)
as a syrup: [R]D +2.5° (c 2, chloroform); IR (neat) 2580, 1240,
Meth yl 5-O-a cetyl-3-O-ben zyl-2-d eoxy-1,4-d ith io-r,â-D-
th r eo-p en t ofu r a n osid e (71). Column chromatography
(ether-hexane 1:3) of the crude product gave 71 (mixture of
stereoisomers) (30%) as a syrup: IR (neat) 1740, 1239, 1082
1
1213, 1137, 1100 cm-1; H NMR (CDCl3) δ 4.37 (d, 1 H, J )
1
cm-1; H NMR (CDCl3) δ 7.38-7.30 (m, 5 H), 5.08 (dd, ∼0.4
5.8 Hz), 4.03 (dd, 1 H, J ) 6.3, 4.7 Hz), 3.95 (dd, 1 H, J ) 6.2,
5.9 Hz), 3.44 (s, 6 H), 3.04 (ddq, 1 H, J ) 7.3, 7.1, 4.9 Hz),
1.78 (d, 1 H, J ) 7.3 Hz), 1.40 (s, 6 H), 1.35 (d, 1 H, J ) 6.9
H, J ) 5.2, 4.9 Hz), 5.03 (dd, ∼0.6 H, J ) 5.0, 4.3 Hz), 4.65-
4.40, 4.27-4.11 (2 m, 5 H), 3.75 (dt, ∼0.6 H, J ) 7.7, 6.0 Hz),

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3959
Hz); 13C NMR (CDCl3) δ 110.4, 105.1, 83.1, 78.3), 56.1, 54.2,
36.7, 27.5, 27.4, 19.7; MS m/z 237 (M+ + 1), 147.
5-S-Acetyl-3-O-ben zyl-6-d eoxy-1,2-O-isop r op ylid en e-5-
th io-â-L-idofu r an ose (41d). Column chromatography (ether-
hexane 1:4) of the crude product gave 41d (87%) as a syrup:
[R]D -33° (c 1, chloroform); IR (neat) 1686, 1216, 1166, 1112,
1075, 1022 cm-1; 1H NMR (CDCl3) δ 7.40-7.30 (m, 5 H), 5.92
(d, 1 H, J ) 3.8 Hz), 4.64 (d, 1 H, J ) 3.8 Hz), 4.60 (AB system,
2 H, J ) 11.8 Hz, δν ) 39.8 Hz), 4.11 (dd, 1 H, J ) 10.1, 3.1
Hz), 3.97 (dq, 1 H, J ) 10.1, 6.8 Hz), 3.89 (d, 1 H, J ) 3.1 Hz),
2.30 (s, 3 H), 1.49, 1.31 (2 s, 6 H), 1.22 (d, 3 H, J ) 6.8 Hz);
13C NMR (CDCl3) δ 195.0, 137.0, 128.5, 128.0, 127.9, 111.6,
104.9, 81.7, 81.5, 81.4, 71.8, 38.5, 30.8, 26.8, 26.3, 18.6; MS
m/z 353 (M+ + 1), 295, 235; MS (calcd mass for C18H24O5S +
H 353.1423) obsd m/z 353.1406.
4-S-Acet yl-3-O-b en zyl-2,5-d id eoxy-4-t h io-a ld eh yd o-D-
th r eo-p en tose Dim eth yl Aceta l (73). Column chromatog-
raphy (ether-hexane 1:1) of the crude product gave 73 (97%)
as a syrup: [R]D +73° (c 2, chloroform); IR (neat) 1689, 1125,
1090, 1056 cm-1; 1H NMR (CDCl3) δ 7.40-7.30 (m, 5 H), 4.64
(AB system, 2 H, J ) 11.7 Hz, δν ) 20.7 Hz), 4.50 (dd, 1 H, J
) 6.6, 5.1 Hz), 3.95 (dq, 1 H, J ) 7.2, 3.2 Hz), 3.64 (ddd, 1 H,
J ) 8.2, 5.1, 3.2 Hz), 3.31, 3.23 (2 s, 6 H), 2.34 (s, 3 H), 1.81-
1.76 (m, 2 H), 1.30 (d, 3 H, J ) 7.3 Hz); 13C NMR (CDCl3) δ
195.4, 138.5, 128.4, 127.9, 127.7, 102.3, 78.0, 72.0, 53.1, 52.8,
40.6, 34.2, 30.8, 15.4.
Gen er a l P r oced u r e for th e Syn th esis of Th iosu ga r s
44, 46, 48, 50, 52, 54, a n d 74. A solution of the S-acetyl
derivative 39a ,c,d , 41a ,c,d , or 73 (2 mmol) in 70% aqueous
acetic acid (20 mL) was heated at ∼80 °C until TLC showed
complete disappearance of the starting material. After cooling,
the reaction mixture was concentrated and coevaporated with
toluene. The crude product was dissolved in anhydrous
methanol (25 mL), and a 0.5 N solution of sodium methoxide
in methanol (0.5 mL) was added. The reaction mixture was
left at rt for 3 h. After deoinization by Amberlite IR-120(H+)
resin the solution was evaporated and the product was
purified.
3-O-Ben zyl-2,5-d id eoxy-4-t h io-a ld eh yd o-D-th r eo-p en -
tose Dim eth yl Aceta l (72). Column chromatography (ether-
hexane 1:1) of the crude product gave 72 (36% from 70) as a
syrup: [R]365 +66° (c 1, chloroform); IR (neat) 2568, 1494, 1451,
1126, 1065, 1028 cm-1 1H NMR (CDCl3) δ 7.38-7.25 (m, 5
;
H), 4.58 (AB system, 2 H, J ) 11.4 Hz, δν ) 19.9 Hz), 4.57
(dd, 1 H, J ) 7.7, 3.1 Hz), 3.57 (dt, 1 H, J ) 7.8, 3.8 Hz), 3.34,
3.31 (2 s, 6 H), 3.18 (m, 1 H), 2.07 (ddd, 1 H, J ) 11.3, 7.7, 3.5
Hz), 1.83 (ddd, 1 H, J ) 11.3, 7.7, 3.5 Hz), 1.62 (d, 1 H, J )
7.5 Hz), 1.35 (d, 3 H, J ) 6.9 Hz); 13C NMR (CDCl3) δ 138.4,
128.4, 127.7, 127.4, 102.1, 80.2, 72.3, 52.9, 52.3, 37.4, 33.6, 20.1.
6-Deoxy-1,2-O-isop r op ylid en e-5-t h io-r-L-ga la ct ofu r a -
n ose (62). Cyclic sulfate 60 was reacted with potassium
thiocyanate following the general procedure described above
for the opening of cyclic sulfates. The corresponding potassium
salt 61 was then treated directly with LiAlH4. Column
chromatography (ether) of the crude product gave 62 (83%
overall yield from 60) as a syrup: [R]D +40° (c 1, methanol),
[lit.84 [R]D +41.7° (c 1, dichloromethane)]; IR (KBr) 3446, 2582,
1
1164, 1069, 1017 cm-1; H NMR (CDCl3) δ 5.84 (d, 1 H, J )
4.0 Hz), 4.52 (d, 1 H, J ) 3.9 Hz), 4.19 (bs, 1 H), 3.68 (dd, 1 H,
J ) 8.5, 3.2 Hz), 3.40 (bs, 1 H), 3.25 (ddq, 1 H, J ) 7.0, 5.2, 3.2
Hz), 2.06 (d, 1 H, J ) 5.2 Hz), 1.49, 1.28 (2 s, 6 H), 1.31 (d, 1
H, J ) 7.0 Hz); 13C NMR (CDCl3) δ 113.0, 104.8, 91.5, 87.3,
76.1, 36.4, 27.2, 26.2, 20.1.
5-S-Acet yl-3-a cet a m id o-3,6-d id eoxy-1,2-O-isop r op y-
lid en e-5-th io-â-L-ta lofu r a n ose (41g). A mixture of 11f (1
mmol) and lithium aluminum hydride (7 mmol) in dry THF
(25 mL) was stirred at rt under an argon atmosphere for 20
h. After cooling, the reaction was mixed with ethyl acetate
(10 mL) and methanol (10 mL), filtered through Celite, and
evaporated The crude product was conventionally acetylated
using Ac2O-Py (5:5 mL). After standard workup, the crude
was purified by column chromatography (ethyl acetate), yield-
ing 41g (55%) as a solid: mp 172-173 °C; [R]D +28° (c 1,
5-Th io-r,â-L-id op yr a n ose (44). Column chromatography
(methanol-chloroform 1:3) of the crude product gave 44 (35%)
(∼1:2 mixture of R/â steroisomers) as a syrup: [R]D +17° (c 1,
methanol) (3 h); IR (neat) 3355, 1269, 1052, 969 cm-1; 1H NMR
(D2O) δ 4.96 (d, J ) 7.1 Hz, H-1R), 4.95 (d, J ) 3.4 Hz, H-1â),
4.10 (dd, J ) 11.5, 6.7 Hz, H-6â), 4.04 (t, J ) 9.7 Hz, H-3R),
4.02 (t, J ) 9.1 Hz, H-3â), 3.92 (dd, J ) 11.5, 4.7 Hz, H-6′â),
3.90 (m, H-6R), 3.88 (t, J ) 9.2 Hz, H-4â), 3.80 (m, H-6′R),
3.78 (dd, J ) 9.3, 3.3 Hz, H-2â), 3.61 (t, J ∼ 8.6 Hz, H-2R),
chloroform); IR (KBr) 1680, 1646, 1548, 1375, 1105, 1024 cm-1
;
1H NMR (CDCl3) δ 5.82 (d, 1 H, J ) 3.6 Hz), 5.73 (d, 1 H, J )
9.9 Hz), 4.59 (dd, 1 H, J ) 4.8, 3.8 Hz), 4.50 (dt, 1 H, J ) 9.3,
4.8 Hz), 3.95-3.86 (m, 2 H), 2.38, 2.06 (2 s, 6 H), 1.59, 1.37 (2
s, 6 H), 1.46 (d, 3 H, J ) 7.0 Hz); 13C NMR (CDCl3) δ 194.5,
169.9, 112.5, 103.9, 81.8, 78.9, 52.7, 39.4, 30.7, 26.7, 26.3, 23.2,
19.3; MS (calcd mass for C13H21O5NS + H 304.1218) obsd m/z
304.1218. Anal. Calcd for C13H21NO5S: C, 51.47; H, 6.98; N,
4.62. Found: C, 51.25; H, 7.10; N, 4.68.
3.56 (t, J ∼ 8.7 Hz, H-4R), 3.20 (m, H-5â), 3.12 (m, H-5R); 13
C
Gen er a l P r oced u r e for th e Acetyla tion of th e Th iol
Der iva tives 40b,c,d a n d 72. The thiol (1 mmol) was acety-
lated overnight at rt with acetic anhydride (4 mL) and pyridine
(2.0 mL). Processing of the mixture by treatment with excess
of methanol and evaporation with several portions of added
methanol followed by toluene gave a crude product.
NMR (D2O) δ 77.6 (C-2R), 75.6 (C-2â), 73.9 (C-3â), 73.5 (C-
1â), 73.3 (C-3R), 73.0 (C-4R), 72.3 (C-1R), 70.2 (C-4â), 61.2 (C-
6â), 59.5 (C-6R), 46.1 (C-5â), 45.8 (C-5R); MS m/z 196 (M+),
178 (M+ - H2O), 160 (M+ - 2 H2O); MS (calcd mass for
C6H12O5S 196.0405) obsd m/z 196.0401.
3-O-Meth yl-5-th io-r,â-L-id op yr a n ose (46). Column chro-
matography (methanol-chloroform 1:5) of the crude product
gave 46 (56%) (∼1:2 mixture of R/â stereoisomers) as a syrup:
[R]D +10° (c 3.4, methanol) (5 min); IR (neat) 3294, 1192, 1105,
3-O-Acetyl-5-S-a cetyl-6-d eoxy-1,2-O-isop r op ylid en e-5-
th io-â-L-idofu r an ose (41a). Column chromatography (ether-
hexane 2:1) of the crude product gave 41a (94%) as a solid:
mp 75 °C; [R]D -13° (c 2, chloroform); IR (KBr) 1747, 1689,
974, 904 cm-1 1H NMR (DMSO-d6) δ 6.18 (d, J ) 7.2 Hz,
;
1
1230, 1097, 1066, 1051, 1023 cm-1; H NMR (CDCl3) δ 5.90
exchangeable with D2O), 5.85 (d, J ) 6.8 Hz, exchangeable
with D2O), 5.13-4.96 (several m, exchangeables with D2O),
4.80-4.71 (m, after isotopic exchange was transformed in two
doublets at δ 4.75, J ) 7.9 Hz and δ 4.70, J ) 2.8 Hz), 3.78-
3.10 (several m), 3.40, 3.39 (2 s, 3 H), 2.99 (m), 2.83 (m); 13C
NMR (DMSO-d6) δ 83.3, 81.3, 76.0, 74.1, 73.7, 71.2, 60.9, 60.6,
59.7, 59.4, 46.0, 44.8; MS m/z 210 (M+), 192, 178, 149.
(d, 1 H, J ) 3.8 Hz), 5.20 (d, 1 H, J ) 2.9 Hz), 4.51 (d, 1 H, J
) 3.8 Hz), 4.20 (dd, 1 H, J ) 9.9, 2.9 Hz), 3.84 (dq, 1 H, J )
9.9, 6.9 Hz), 2.34, 2.14 (2 s, 6 H), 1.51, 1.30 (2 s, 6 H), 1.29 (d,
3 H, J ) 7.0 Hz); 13C NMR (CDCl3) δ 194.7, 169.8, 112.1, 104.5,
83.5, 80.3, 75.9, 37.9, 30.7, 26.6, 26.1, 20.8, 18.2; MS m/z 305
(M+ + 1), 247, 187; MS (calcd mass for C30H20O6S + H
305.1059) obsd m/z 305.1048.
3-O-Ben zyl-5-th io-r,â-L-id op yr a n ose (48). Column chro-
matography (methanol-chloroform 1:7) of the crude gave 48
(57%) as a solid: mp 102-103 °C (from ether); [R]D +9°, [R]436
+18° (5 min), [R]D +5°, [R]436 +12° (24 h) (c 2, methanol); IR
5-S-Acetyl-6-d eoxy-1,2-O-isop r op ylid en e-3-O-m eth yl-5-
th io-â-L-idofu r an ose (41c). Column chromatography (ether-
hexane 1:3) of the crude product gave 41c (86%) as a syrup:
[R]D -44° (c 3, chloroform); IR (neat) 1686, 1215, 1167, 1116,
1080, 1021 cm-1; 1H NMR (CDCl3) δ 5.89 (d, 1 H, J ) 3.9 Hz),
4.60 (d, 1 H, J ) 3.9 Hz), 4.08 (dd, 1 H, J ) 10.2, 3.1 Hz), 3.90
(dq, 1 H, J ) 10.2, 6.8 Hz), 3.66 (d, 1 H, J ) 3.1 Hz), 3.42 (s,
3 H), 2.32 (s, 3 H), 1.49, 1.32 (2 s, 6 H), 1.32 (d, 3 H, J ) 6.8
Hz); 13C NMR (CDCl3) δ 195.0, 111.6, 104.9, 83.8, 81.5, 81.2,
57.6, 38.5, 30.8, 26.8, 26.3, 18.2; MS m/z 277 (M+ + 1), 261,
219, 159; MS (calcd mass for C12H20O5S + H 277.1109) obsd
m/z 277.1087.
1
(KBr) 3314, 1118, 1101, 1066, 1026 cm-1; H NMR (D2O, 500
MHz) δ 7.45-7.18 (m, Ph), 5.00 (d, J ) 2.5 Hz, H-1â), 4.98 (d,
J ) 7.7 Hz, H-1R), 4.76-4.70 (m, PhCH2), 4.14 (dd, J ) 7.0,
5.0 Hz, H-4R), 4.13 (dd, J ) 7.5, 5.1 Hz, H-4â), 4.07 (dd, J )
11.3, 6.7 Hz, H-6â), 3.95 (dd, J ) 11.5, 4.8 Hz, H-6R), 3.93-
3.86 (m, H-2â,3â,6′â), 3.81 (dd, J ) 11.6, 8.0 Hz, H-6′R), 3.79
(t, J ) 7.7 Hz, H-2R), 3.62 (t, J ) 8.0 Hz, H-3R), 3.24 (m,
H-5R,â); 13C NMR (D2O, 100 MHz) δ 139.5, 139.2, 129.3, 128.6,
128.1, 127.8, 127.1, 125.7 (C6H5), 81.0 (C-3R), 79.5 (C-3â), 76.0

3960 J . Org. Chem., Vol. 62, No. 12, 1997
Calvo-Flores et al.
(C-2R), 75.1 (PhCH2â), 74.9 (C-2â), 74.7 (PhCH2R), 73.7 (C-
1â), 73.0 (C-1R), 72.3 (C-4R,â), 61.3 (C-6â), 60.1 (C-6R), 46.1
(C-5â), 44.5 (C-5R); MS m/z 269 (M+ + 1 - H2O), 25, 161, 145,
143; MS (FAB) m/z 287 (M+ + 1). Anal. Calcd for C13H18O5S:
C, 54.53; H, 6.34; S, 11.20. Found: C, 54.36; H, 6.45; S, 11.19.
6-Deoxy-5-th io-r,â-L-id op yr a n ose (50). Column chro-
matography (methanol-chloroform 1:3) of the crude product
gave 50 (90%) (∼1:1.3 mixture of R/â steroisomers) as a
syrup: [R]D -11° (5 min), -9.5° (24 h) (c 1, water); IR (neat)
3378, 1076, 1053, 1010 cm-1; 1H NMR (D2O, 400 MHz) δ 5.01
(d, J ) 3.2 Hz, H-1â), 4.89 (d, J ) 8.2 Hz, H-1R), 3.95-3.87
(m, H-4R, H-4â, H-3â), 3.78 (dd, J ) 8.5, 3.2 Hz, H-2â), 3.60-
3.53 (m, H-2R, H-3R), 3.11-3.06 (m, H-5R,â), 1.47 (d, J ) 7.4
Hz, Me â-anomer), 1.36 (d, J ) 7.4 Hz, Me R-anomer); 13C NMR
(D2O) δ 78.1 (C-2R), 75.7 (C-2â), 74.9 (C-4â), 74.6 (C-1â), 74.5
(C-4R), 72.5 (C-3R), 71.8 (C-1R), 69.3 (C-3â), 39.0 (C-5R), 37.9
(C-5â), 17.4 (C-6R), 14.7 (C-6â); MS m/z 186 (M+), 169; MS
(calcd mass for C6H12O4S 186.0405) obsd m/z 186.0401.
6-Deoxy-3-O-m eth yl-5-th io-r,â-L-id op yr a n ose (52). Col-
umn chromatography (ether) of the crude product gave 52
(62%) (∼1:1.25 mixture of R/â steroisomers) as a syrup: [R]D
-7.5° (c 2.1, methanol) (5 min); IR (neat) 3398, 1232, 1051,
1â), 78.0 (C-2R), 74.7 (C-1R), 41.9 (C-4â), 40.0 (C-4R), 19.6 (C-
5R), 17.7 (C-5â); MS m/z (CI+) 150 (M+), 132 (M+ - H2O), 114
(M+ - 2 H2O); HRMS (EI+) calcd for C5H10O3S 150.0351 (M+),
found 150.0346.
Syn th esis of 6-Deoxy-5-th io-r,â-L-ga la ctop yr a n ose (5-
Th io-r,â-L-fu cose) (63). A solution of 62 (2.31 mmol) in 50%
aqueous acetic acid (10 mL) was heated at 75 °C for 3 h. After
cooling, the reaction mixture was concentrated and coevapo-
rated with toluene, yielding a crystalline residue that was
recrystallized from methanol to give 63 (R-anomer) (250 mg):
mp 159-160 °C (lit.84 mp 159-160 °C); [R]D -200° (5 min) and
[R]D -210° (2 d) (c 1, water) [lit.84 [R]D -259.1° (5 min) and
1
[R]D -233.0 (2 days) (c 1.2, water)]; H NMR (D2O, 400 MHz)
δ 4.90 (d, 1 H, J ) 3.2 Hz, H-1), 4.04 (bs, 1 H, H-4), 3.93 (dd,
1 H, J ) 10.2, 3.2 Hz, H-2), 3.80 (dd, 1 H, J ) 10.2, 2.9 Hz,
H-3), 3.49 (q, 1 H, J ) 7.0 Hz, H-5), 1.09 (d, 1 H, J ) 7.0 Hz,
Me); 13C NMR (D2O, 100 MHz) δ 75.6 (C-4), 75.1 (C-1), 72.1
(C-2), 71.5 (C-3), 37.4 (C-5), 17.0 (C-6); 13C NMR (DMSO-d6,
75 MHz) δ 74.3 (C-4), 73.9 (C-1), 71.0 (C-2), 70.1 (C-3), 36.3
(C-5), 16.7 (C-6). The mother liquors were purified by column
chromatography (methanol-chloroform 1:3), giving 63 (∼3.7:1
mixture of R/â anomers) (105 mg) (85% overall yield) as a
solid: 1H NMR (DMSO-d6 + D2O, 300 MHz) δ 4.62 (d, J ) 3.1
Hz, H-1R), 4.45 (d, J ) 8.8 Hz, H-1â), 3.75 (dd, 1 H, J ) 2.7,
1.6 Hz, H-4R), 3.67 (dd, J ) 10.0, 3.1 Hz, H-2R), 3.64 (m, H-4â),
3.53 (dd, J ) 10.0, 3.9 Hz, H-3R), 3.47 (dd, J ) 10.0, 8.8 Hz,
H-2â), 3.29 (dq, J ) 7.0, 1.6 Hz, H-5R), 3.10 (dd, J ) 9.6, 2.9
Hz, H-3â), 3.01 (dq, J ) 7.0, 1.6 Hz, H-5â), 1.06 (d, J ) 7.1
Hz, Me of the R-anomer), 1.05 (d, J ) 7.1 Hz, Me of the
â-anomer).
1
1030, 970 cm-1; H NMR (D2O, 500 MHz) δ 5.02 (d, J ) 3.1
Hz), 4.89 (d, J ) 8.3 Hz), 4.01 (dd, J ) 8.2, 4.6 Hz), 3.99 (dd,
J ) 8.6, 4.7 Hz), 3.87 (dd, J ) 9.2, 3.3 Hz), 3.69 (dd, J ) 8.4,
8.0 Hz), 3.60 (s), 3.59 (dd, J ) 9.2, 8.8 Hz), 3.58 (s), 3.32 (dd,
J ) 8.6, 8.4 Hz), 3.12 (m), 1.48 (d, J ) 7.4 Hz), 1.37 (d, J ) 7.4
Hz); 13C NMR (DMSO-d6) δ 82.8, 80.4, 80.4, 76.7, 74.5, 73.1,
73.0, 59.1, 59.8, 38.6, 37.0, 17.4, 15.4; MS m/z 194 (M+), 176,
162.
Gen er a l P r oced u r e for th e Acetyla tion of Th iosu ga r s
44, 46, 48, 50, 52, a n d 54. The thiosugar (1 mmol) (R/â
mixture of steroisomer for 44, 46, 50, 52, 54 and â steroisomer
for 48) was acetylated overnight at rt with acetic anhydride
(4 mL) and pyridine (2.0 mL). Processing of the mixture by
treatment with excess of methanol and evaporation with
several portions of added methanol followed by toluene gave
a crude product.
3-O-Ben zyl-6-d eoxy-5-th io-r,â-L-id op yr a n ose (54). Col-
umn chromatography (ether) of the crude product gave 54
(65%) (∼1:2 mixture of R/â steroisomers) as a syrup: [R]D
-11.0° (c 1.6, methanol) (5 min); IR (neat) 3393, 1209, 1096,
1075, 1028 cm-1; 1H NMR (D2O, 500 MHz) δ 7.45-7.18 (m, 5
H, Ph), 5.07 (d, J ) 2.5 Hz, H-1â), 4.90 (d, J ) 7.8 Hz, H-1R),
4.86-4.78 (m, PhCH2), 4.08 (dd, J ) 8.0, 4.1 Hz, H-4R), 3.97
(dd, J ) 7.5, 4.2 Hz, H-4â), 3.93 (dd, J ) 7.9, 2.8 Hz, H-2â),
3.88 (t, J ) 7.7 Hz, H-3â), 3.76 (t, J ) 7.9 Hz, H-2R), 3.59 (t,
J ) 8.0 Hz, H-3â), 3.20 (m, H-5R,â), 1.46 (d, J ) 7.2 Hz, Me of
â-anomer), 1.26 (d, J ) 7.3 Hz, Me of R-anomer); 13C NMR
(D2O) δ 139.3, 139.2, 130.3, 130.2, 130.1 130.1, 129.8, 129.3,
128.9 (C6H5), 82.1(C-3R), 80.0 (C-3â), 80.0 (C-2â), 77.3 (C-2R),
75.5 (C-1â), 74.7 (C-4R,â), 74.2 (C-1R), 76.0, 75.9 (PhCH2), 40.2
(C-5R), 38.1 (C-5â), 18.6 (Me of â-anomer), 16.4 (Me of
1,2,3,4,6-P en ta -O-a cetyl-5-th io-r,â-
L-id op yr a n ose (45).
Column chromatography (ether-hexane 1:1) of the crude
product gave 45 (94%) as a solid. Physical properties ([R]D,
IR, 1H and 13C NMR) are identical to those described in
literature82 for this compound.
1,2,4,6-Tetr a -O-a cetyl-3-O-m eth yl-5-th io-r,â-L-id op yr a -
n ose (47). Column chromatography (ether-hexane 1:1) of the
crude product gave 47 (98%) (2.2:1 mixture of â/R steroisomers)
as a solid: mp 78-87 °C; [R]D +43° (c 1, chloroform); IR 1736,
R-anomer); MS m/z 270 (M+), 252 (M+ - H2O), 239 (M+
-
CH3O), 185 (M+ - C3H5OS); HRMS (EI+) calcd for C13H18O4S
270.0926 (M+), found 270.0922.
1
1216, 1114, 1032, 945 cm-1; H NMR (CDCl3) δ 6.07 (d, J )
3.5 Hz, H-1â), 5.97 (d, J ) 6.0 Hz, H-1R), 5.25 (dd, J ) 10.0,
5.4 Hz, H-4â), 5.23-5.18 (m, H-2,4R), 5.13 (dd, J ) 9.8, 3.5
Hz, H-2â), 4.54 (dd, J ) 11.5, 8.0 Hz, H-6â), 4.48 (dd, J ) 11.5,
6.3 Hz, H-6′â), 4.29 (dd, J ) 11.4, 6.7 Hz, H-6R), 4.21 (dd, J )
11.3, 6.2 Hz, H-6′R), 3.69 (t, J ) 10.0 Hz, H-3â), 3.67-3.42
(m, H-5â, H-3,5R), 3.52 (s, MeOâ), 3.48 (s, MeOR), 2.16-2.06
(6 s, 4 MeCO); 13C NMR (CDCl3) δ 170.5, 170.0, 169.6, 169.0
(4 CO), 75.8 (C-3â), 74.7 (C-2â), 74.6 (C-4â), 72.3 (C-1â), 77.2
(C-3R), 71.4 (C-1R), 69.7 (C-2R), 69.6 (C-4R), 64.1 (C-6â), 62.6
(C-6R), 61.3 (MeOâ), 59.6 (MeOR), 41.0 (C-5â), 37.0 (C-5R),
21.1, 20.9, 20.8, 20.7 (MeCO). Anal. Calcd for C15H22O9S: C,
47.61; H, 5.86; S, 8.47. Found: C, 47.91; H, 6.03; S, 8.51.
1,2,4,6-Tet r a -O-a cet yl-3-O-b en zyl-5-t h io-â-L-id op yr a -
n ose (49). Column chromatography (ether-hexane1:3) of the
crude product gave 49 (76%) as a solid: mp 112-120 °C; [R]D
+66° (c 1, chloroform); IR (neat) 1734, 1222, 1116, 1054, 1025,
940 cm-1; 1H NMR (CDCl3) δ 7.40-7.26 (m, 5 H, Ph), 6.09 (dd,
J ) 3.4, 0.7 Hz, H-1), 5.34 (dd, J ) 9.9, 5.4 Hz, H-4), 5.22 (dd,
J ) 9.9, 3.4 Hz, H-2), 4.72 (bs, 2 H, PhCH2), 4.55 (dd, J )11.5,
7.8 Hz, H-6), 4.50 (dd, J ) 11.5, 6.4 Hz, H-6′), 4.00 (t, J ) 9.9
Hz, H-3), 3.48 (dq, J ) 7.0, 0.7 Hz, H-5), 2.16, 2.07, 2.01, 1.95
(4 s, 12 H, 4 MeCO); 13C NMR (CDCl3) δ 170.5, 169.5, 169.5,
169.0 (4 CO), 138.0, 128.4, 127.5, 127.3 (C6H5), 75.9 (PhCH2),
74.8 (C-2), 74.7 (C-3), 74.6 (C-4), 72.3 (C-1), 64.1 (C-6), 41.0
(C-5), 21.1, 20.8, 20.6 (4 MeCO). Anal. Calcd for C21H26O9S:
C, 55.49; H, 5.77; S, 7.05. Found: C, 55.75; H, 5.92; S, 6.80.
1,2,3,4-Te t r a -O-a ce t yl-6-d e oxy-5-t h io-r,â-L-id op yr a -
n ose (51). Column chromatography (ether-hexane 1:1) of the
3-O-Ben zyl-2,5-d id eoxy-4-t h io-r,â-D-th r eo-p en t ofu r a -
n ose (74). Column chromatography (ether-hexane 1:1) of the
crude product gave 74 (70%) (∼1.4:1 mixture of R/â steroiso-
mers) as a syrup: [R]D +30° (5 min); 1H NMR (CDCl3) δ 7.40-
7.25 (m), 5.48-5.42 (m), 4.68-4.52 (m), 4.35 (dt, J ) 9.3, 5.4
Hz), 4.08 (m), 3.69 (dq, J ) 6.9, 6.0 Hz), 3.60 (bs), 3.54 (dq, J
) 6.8, 3.9 Hz), 2.61 (dd, J ) 13.9, 1.1 Hz), 2.42 (bs), 2.32 (ddd,
J ) 13.2, 9.2, 5.3 Hz), 2.19 (ddd, J ) 13.2, 5.0, 2.6 Hz), 1.97
(ddd, J ) 13.9, 4.9, 3.0 Hz), 1.48 (d, J ) 6.8 Hz), 1.23 (d, J )
7.0 Hz); 13C NMR (CDCl3) δ 137.5, 128.6, 128.5, 128.1, 127.9,
127.8, 127.6, 127.0, 83.9, 83.3, 81.5, 65.3, 72.0, 48.7, 44.4, 43.1,
41.9, 17.0, 16.0.
Syn th esis of 5-Deoxy-4-th io-r,â-L-ar abin ofu r an ose (56).
A solution of 43b (1.5 mmol) in 70% aqueous acetic acid (6
mL) was heated at ∼55 °C for 40 h. After cooling, the reaction
mixture was concentrated and coevaporated with toluene. The
crude product was purified by column chromatography (metha-
nol-chloroform 1:10). Eluted first was a complex mixture (70
mg, Rf ) 0.7 in methanol:chloroform 1:7) that was not further
investigated. Eluted second was 27b (120 mg, 54%) (∼1.4:1
mixture of R/â steroisomers) as a syrup: IR (neat) 3352, 1098,
1
1067, 1026, 298 cm-1; H NMR (D2O) δ 5.24 (d, J ) 6.0 Hz,
H-1â), 5.12 (d, J ) 4.7 Hz, H-1R), 3.95 (dd, J ) 10.1, 4.7 Hz,
H-2R), 3.93 (dd, J ) 8.9, 6.0 Hz, H-2â), 3.80 (dd, J ) 10.0, 8.7
Hz, H-3R), 3.58 (t, J ) 9.0 Hz, H-3â), 3.43 (dq, J ) 9.3, 6.4 Hz,
H-4â), 3.09 (dq, J ) 8.7, 6.5 Hz, H-4R), 1.39 (d, J ) 6.6 Hz,
Me of R-anomer), 1.31 (d, J ) 6.4 Hz, Me of â-anomer); 13C
NMR (D2O) δ 83.4 (C-2â), 80.4 (C-3â), 79.8 (C-3R), 78.5 (C-

Applications of Cyclic Sulfates of vic-Diols
J . Org. Chem., Vol. 62, No. 12, 1997 3961
crude product gave 51 (73%) (∼1:1.5 mixture of R/â steroiso-
mers) as a solid: mp 75-77 °C; [R]D +28° (c 1, chloroform); IR
the crude product gave 55 (90%) (∼1:2 mixture of R/â steroi-
somers) as a solid: mp 59-65 °C; [R]D +50° (c 1, chloroform);
1
(neat) 1750, 1219, 1030 cm-1; H NMR (CDCl3, 400 MHz) δ
IR (neat) 1748, 1247, 1116, 998, 943, 911 cm-1 1H NMR
;
6.10 (d, J ) 3.5 Hz, H-1â), 5.93 (d, J ) 7.2 Hz, H-1R), 5.60 (t,
J ) 10.3 Hz, H-3â), 5.23 (dd, J ) 10.3, 5.6 Hz, H-4â), 5.20 (dd,
J ) 10.4, 3.6 Hz, H-2â), 5.22-5.19 (m, H-2,3R), 5.15 (dd, J )
7.8, 3.9 Hz, H-4R), 3.40 (dq, J ) 7.3, 3.8 Hz, H-5R), 3.24 (dq,
J ) 7.3, 5.6 Hz, H-5â), 2.15-1.99 (8 s, 4 MeCO), 1.53 (d, J )
7.4 Hz, Me of â-anomer), 1.37 (d, J ) 7.3 Hz, Me of R-anomer);
13C NMR (CDCl3) δ 169.9-168.8 (eigth peaks, CO), 74.1 (C-
4â), 73.2 (C-2R), 72.3 (C-4R), 72.2 (C-1â), 70.9 (C-2â), 70.8 (C-
1R), 69.3 (C-3R), 66.3 (C-3â), 37.0 (C-5â), 34.1 (C-5R), 21.1-
20.5 (five peaks, MeCO), 18.0 (C-6â), 15.4 (C-6R); MS m/z 348
(M+), 289, 228, 186. Anal. Calcd for C14H20O8S: C, 48.27; H,
5.79; S, 9.20. Found: C, 48.20; H, 5.79; S, 8.80.
1,2,4-Tr i-O-acetyl-6-deoxy-3-O-m eth yl-5-th io-r,â-L-idopy-
r a n ose (53). Column chromatography (ether-hexane 1:1) of
the crude product gave 53 (90%) (∼1:2 mixture of R/â steroi-
somers) as a solid: mp 40-46 °C; [R]D +49.6° (c 1, chloroform);
IR (neat) 1750, 1219, 1030 cm-1; 1H NMR (CDCl3) δ 6.09 (bd,
J ) 3.6 Hz, H-1â), 5.85 (d, J ) 5.7 Hz, H-1R), 5.18 (dd, J )
9.9, 5.0 Hz, H-2R), 5.17 (dd, J ) 10.0, 4.9 Hz, H-4â), 5.14 (dd,
J ) 9.9, 3.6 Hz, H-2â), 5.09 (dd, J ) 5.8, 3.3 Hz, H-4R), 3.74
(t, J ) 9.8 Hz, H-3â), 3.54-3.45 (m, H-3,5R), 3.51 (s, OMeâ),
3.48 (s, OMeR), 2.14, 2.13, 2.10, 2.06 (4 s, 3 MeCO), 1.50 (d, J
) 7.4 Hz, Me of â anomer), 1.28 (d, J ) 7.2 Hz, Me of R
anomer); 13C NMR (CDCl3) δ 170.2-169.1 (six peaks, 3 CO),
77.3 (C-3R), 75.8 (C-4â), 75.4 (C-3â), 74.8 (C-2â), 72.8 (C-1â),
72.2 (C-4R), 71.9 (C-1R), 69.2 (C-2R), 61.0 (OMeâ), 59.4 (OMeR),
36.9 (C-5â), 32.6 (C-5R), 21.2, 20.0, 20.9, 20.8 (MeCO), 18.1
(C-6â), 15.5 (C-6R). Anal. Calcd for C13H20O7S: C, 48.74; H,
6.29; S, 10.01. Found: C, 49.19; H, 6.43; S, 10.28.
(CDCl3) δ 7.40-7.30 (m, Ph), 6.12 (d, J ) 3.5 Hz, H-1â), 5.86
(d, J ) 5.5 Hz, H-1R), 5.30-5.20 (m, H-2,4â, H-2R), 5.14 (dd,
J ) 5.6, 3.1 Hz, H-4R), 4.73 (s, PhCH2â),. 4.68 (s, PhCH2R),
4.02 (t, J ) 9.7 Hz, H-3â), 3.79 (t, J ) 5.6 Hz, H-3R), 3.59 (dq,
J ) 7.2, 3.2 Hz, H-5R), 3.28 (dq, J ) 7.4, 5.1 Hz, H-5â), 2.14,
2.02, 1.96 (3 s, MeCOâ), 2.08, 2.05, 2.03 (3 s, MeCOR), 1.51
(d, J ) 7.3 Hz, Me of â anomer), 1.27 (d, J ) 7.2 Hz, Me of R
anomer); 13C NMR (CDCl3) δ 170.2-169.1 (six peaks, 3 CO),
138.2-127.3 (eight peaks, C6H5), 75.9 (C-4â), 74.9 (C-2â), 74.3
(C-3â), 72.9 (C-1â), 75.4 (C-3R), 72.2 (C-2R), 72.1 (C-1R), 69.0
(C-4R), 75.6 (PhCH2 of the â anomer), 73.6 (PhCH2 of the R
anomer), 37.0 (C-5â), 32.4 (C-5R), 21.1, 20.9, 20.7 (MeCO), 18.1
(C-6â), 15.8 (C-6R). Anal. Calcd for C19H24O7S: C, 57.56; H,
6.10; S, 8.09. Found: C, 57.58; H, 6.39; S, 8.36.
Ack n ow led gm en t. We thank the Comision Asesora
de Investigacio´n Cient´ıfica y Te´cnica for financial sup-
port (Proyect No. PB92/0936). Dr. A. Vargas-Berenguel
(Universidad de Almeria, Spain) is also acknowledged
for his suggestions during the preparation of this paper.
Su p p or tin g In for m a tion Ava ila ble: NMR (1H and 13C)
spectra for new substances that were not characterized by
combustion analysis or high-resolution MS (40 pages). This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
for ordering information.
1,2,4-Tr i-O-acetyl-6-deoxy-3-O-ben zyl-5-th io-r,â-L-idopy-
r a n ose (55). Column chromatography (ether-hexane 1:2) of
J O962066B