Diastereoisomerically pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, crystal structure, absolute configuration and reactivity

Article abstract of DOI:10.3390/molecules25153392

The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-Oisopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P2₁2₁2₁, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.

Full text of DOI:10.3390/molecules25153392

molecules
Article
Diastereoisomerically Pure, (S)-O-1,2-O-isopropyli
dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate:
Synthesis, Crystal Structure, Absolute Configuration
and Reactivity
Bogdan Bujnicki , Jarosław Błaszczyk * , Marek Chmielewski and Józef Drabowicz 1,3,
1
1,
2
*
1
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Division of
Organic Chemistry, Sienkiewicza 112, 90–363 Łód z´ , Poland; bogbujni@cbmm.lodz.pl
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01–224 Warszawa, Poland;
marek.chmielewski@icho.edu.pl
Institute of Chemistry, Jan Długosz University, Aleja Armii Krajowej 13/15, 42–200 Cz e˛ stochowa, Poland
Correspondence: blaszcz8@cbmm.lodz.pl (J.B.); draj@cbmm.lodz.pl (J.D.);
Tel.: +48-(42)-6803319 (J.B.); +48-(42)-6803234 (J.D.)
2
3
*
ꢀ
ꢁꢂꢀꢃꢄꢅꢆꢇ
ꢀ
ꢁꢂꢃꢄꢅꢆ
Received: 1 July 2020; Accepted: 23 July 2020; Published: 27 July 2020
Abstract: The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-O-
isopropylidene-3,5-O-sulfinyl- -d-glucofuranose (R)- was found to be stopped at the stage
of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O- -d-glucofuranosyl)
α
4
α
t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was
determined by X-ray crystallography. Comparison of the absolute configurations of the starting
sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group
P2 2 2 , with the single compound molecule present in the asymmetric unit), clearly indicates that
1
1 1
the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with
the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which
both the entering and leaving groups are located in apical positions.
Keywords: diastereoisomeric sulfites and sulfinates; sulfinylation; crystal structure; X-ray crystallography;
single-crystal diffractometry; absolute configuration; retention and inversion
1
. Introduction
Racemic and optically active diastereoisomeric and/or enantiomeric sulfinic esters played a very
important role in the development of sulfur chemistry and especially sulfur stereochemistry [1–15].
Preparation of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a by reacting p-toluenesulfinyl
chloride 1a with (-)-(1R,3S,5R)-menthol in the presence of pyridine (Scheme 1) [16], confirmed for
the first time stereogenity of a sulfinyl sulfur atom and its optical stability at room temperature [2,3].
It is worth noting that very recently diasteroisomerically pure sulfinate 3a was isolated in almost
quantitative yield by reacting p-toluenesulfinyl chloride 1a with (-)-(1R,3S,5R)-menthol in the absence
of a base as an HCl scavenger [17], while all attempts of its isolation under flow conditions resulted in
the formation of 2a/3a mixtures [18].
Molecules 2020, 25, 3392; doi:10.3390/molecules25153392
www.mdpi.com/journal/molecules

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Scheme 1. Synthesis of diastereoisomeric O-menthyl p-toluenesulfinates 2a/3a.
This sulfinate was used as a precursor of the first enantiomerically pure sulfoxide, i.e., ethyl p-tolyl
sulfoxide [19 21]. Subsequently, the reaction of this diastereoisomeric sulfinates with organometallic
reagents has been commonly applied to obtain a very rich family of enantiomerically pure sulfoxides
and other sulfinyl derivatives as “Andersen synthesis” [ ]. Following sulfinylation of the hydroxyl
–
1–8
groups of a sugar moiety was used to prepare other diastereomeric sulfinates, which are used again as
substrates for the synthesis of enantiomerically pure sulfinyl derivatives. The best results were obtained
with diacetone
α
-d-glucose (DAG) and its cyclohexyl analogue, dicyclohexylidene
α
-d-glucose (DCG)
(Scheme 2) [22–27].
O
S
O
S
O
S
*
ROH
R1
Cl
* OR*
*RO *
R1
2b, c
R1
a or b
1
1
3b, c
R = alkyl, aryl
O
O
*
*
b=ROH =
O
a=ROH =
O
O
O
O
O
O
HO
HO
O
dicyclohexylidene -D-glucose (DCG)
diacetone -D-glucose (DAG)
Scheme 2. Sulfinylation of dicyclohexylidene α-d-glucose (DCG) and diacetone α-d-glucose (DAG).
In the search for an alternative and new procedure for the preparation of diastereomeric
sulfinates derived from readily available sugars, we focused our attention on diastereomerically
pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 [28] (Figure 1) and its reactivity
with organometallic reagents.
Figure 1. (R)-1,2-O -isopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4.
The possibility of using this diastereoisomerically pure sulfite for the preparation of selected
diastereoisomeric O-sulfinates results from our earlier observation that the reaction of prochiral sulfites

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with t-butylmagnesium chloride could be stopped on the stage of the corresponding sulfinic esters [29
and from the synthesis of enantiomerically enriched t-butanesulfinates by the reaction of prochiral
sulfites with t-butylmagnesium chloride carried out in the presence of optically active aminoalcohols
as a chiral complexing agent (Scheme 3) [30].
]
6
5
Scheme 3. Synthesis of enantiomerically enriched t-butanesulfinates 6.
2
. Results and Disscusion
Having in the hands diastereomerically pure (R)-1,2-O-isopropylidene-3,5-O-sulfinyl-
d-glucofuranose (R)- , synthesized from -d-glucofuranose in the sequence of reactions, described
earlier by one of us [28], we decided to check if its reactions with Grignard reagents could be stopped
at the stage of the corresponding sulfinic acid esters. Reactions of with methylmagnesium iodide
, phenylmagnesium bromide 7b, and p-tolylmagnesium bromide 7c did not afford optically active
α
-
4
α
4
7
a
sulfinates 8a
assuming that precursors of sulfinates 8a
–
c
, but symmetrical sulfoxides 9a
–
c
were obtained as products. This can be explained by
0
–c, magnesium functionalized sulfinates 8 a
–c
generated in
the first stage of the reaction, react immediately with another equivalent of Grignard reagents present
in the reaction mixture (Scheme 4). In the case of benzylmagnesium bromide 7d, 1,2-diphenylethane
was isolated as the main product. On the other hand, the reaction of (R)-4 with t-butylmagnesium
chloride 7e stopped at the stage of sulfinate 10. When tetrahydrofuran, diethyl ether and benzene were
used as solvents, the product was isolated as a single diastereoisomer, in 88%, 90%, and 85% yield,
respectively (Scheme 5).
Scheme 4. Reactions of sulfite (R)-4 with Grignard reagents 7a–d.

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OH
OH
O
S
t-BuMgCl
O
O
7
e
O
O
S
O
O
Bu-t
HO
O
O
O
O
(
R)-4
(S)-
10
THF
Et O
2
88%
90%
Benzene 85%
Scheme 5. Fully diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium chloride 7e.
Analytically pure sulfinate (-)-10 was isolated by column chromatography (DCM: Et O 1:1).
2
Its 100% diastereoselective purity was confirmed by conversion (under conditions that preclude
racemization of the substrate and product) into the known enantiomerically pure t-butyl methyl
sulfoxide (+)-(R)-11 (Scheme 6) [25,31]. Given that the configuration at the stereogenic sulfur atom of
sulfinate 10 is inverted during this reaction, its (S) absolute configuration could be suggested.
OH
O
S
MeMgI
7a
O
S
O
O
Bu-t
O
Bu-t
Me
HO
-)-(S)-10
O
(
+)-(R)-11
(
Scheme 6. Fully stereoselective reaction of sulfinate (S)-10 with methymagnesium iodide 7a.
It is interesting to note that the reaction of sterically demanded Grignard reagents (such
as 1-adamantylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, or 2,4,6-tri-tert-
butylphenylmagnesium bromide) with diastereoisomerically pure sulfite (R)-
an excess of organometallics was used, and the reaction time at room temperature was prolonged up
to 7 days. In these cases, the sulfite (R)- was recovered and the Grignard reagent used was converted
into the corresponding hydrocarbon during reaction work-up. It should be noted that the recovery
4 did not occur, even if
4
of diastereoisomerically pure sulfite (R)-4 indicates simultaneously a lack of racemization under the
reaction conditions
To prove without a doubt the absolute configuration of sulfinate (-)-(S)-10 based on the
chemical correlation discussed above its structure and absolute configuration at the stereogenic
sulfur atom were determined by an X-ray structural analysis (see Figure 2). (S)-1,2-O-isopropylidene-
(5-O-
α-d-glucofuranosyl) t-butanesulfinate (S)-10 crystallizes in an orthorhombic system, in space
group P2 2 2 (Table S1 in SI). The unit cell consists of four monomers. The absolute configuration at
1
1 1
the chiral sulfur atom is S. The five-membered ring C1,C2,C3,C4,O4 adopts a half-chair conformation,
while the ring C1,C2,O2,C7,O1 is an envelope, with the O2 atom being at the flap position. The angle
◦
of envelope opening is equal to 29.7 . The calculated values of the asymmetry parameters [32
both rings are collected in Table S2 (see SI).
,33] for

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Figure 2. Molecular structure of (S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate
. The thermal ellipsoids are shown with 50% probability. Temperature of data collection was 100 K.
1
0
The free electron pair at the sulfur atom is behind the Figure plane.
Comparison of the absolute configurations of the starting sulfite, (R)-1,2-O-isopropylidene-3,
5-O-sulfinyl-α-d-glucofuranose (R)-4, and the structure of the corresponding (S)-1,2-O-isopropylidene-
(
5-O- -d-glucofuranosyl) t-butanesulfinate (S)-10 formed, clearly indicates that nucleophilic
α
substitution at the stereogenic sulfur atom occurs with the full inversion of configuration. This can be
explained by the reaction sequence which is shown below in the Scheme 7 and by assumption that the
intermediate 4C has a trigonal bipyramidal structure. According to this mechanistic proposal, discussed
in details in our recent paper [34], the observed inversion of configuration is caused by the presence
of both the entering t-butyl substituent and the leaving O-α-d-glucofuranosyl group in the apical
positions of this intermediate. This mechanistic proposal (in which we assume the monomeric nature
of t-butylmagnesium chloride) also explains why the regioisomeric t-butanesulfinate 12, the formation
of which, via the intermediate 4E, is shown in the upper part of Scheme 7 was not observed in all
experiments carried out in THF, Et O, nor benzene. This is because the formation of the 4E intermediate
2
is unfavorable due to the steric repulsion between t-butyl group and O-α-d-glucofuranosyl group in
an equatorial position.
Scheme 7. Proposed mechanism for diastereoselective reaction of sulfite (R)-4 with t-butylmagnesium
chloride.
An interesting feature, which is shown in Figure 2, is the presence of a strong O-H...O interaction
between oxygen atoms O3 and O11. The distance O3—O11 is 2.888 Å (for other details, see Figure 3).

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This might be related to the inversion of configuration of the S atom. Besides the intramolecular
O3-H(3)—O11 hydrogen bond, there is also an intermolecular O6-H(6)...O3SYM (1+x, y, z) hydrogen
bond, building a linear chain parallel to the a axis. The distance O6—O3SYM is 2.800 Å (for other
details, see Figure 3).
Figure 3. The two strong O-H...O interactions between oxygen atoms: O3 and O11 (intramolecular)
and between O6 and O3SYM (intermolecular, SYM = 1 + x,y,z), in the crystal lattice of
(S)-1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate 10. The interaction between
O6 and O3SYM creates a linear chain extending through entire lattice along a axis. The distance
O3—O11 is 2.888 Å, and the distance O6—O3SYM is 2.800 Å.
Figure 2 presents the large ellipsoids of the atoms of terminal groups (atom C7 and its attachments
C71, C72), most likely due to the increased mobility of that region. This mobility increase seems to be
an effect of the involvement of the remaining (stable) region of the molecule in two strong intra- and
intermolecular hydrogen bonding systems which result in good stability. Therefore, the regions which
are not involved in that H-bonding system are forced to be highly mobile.
3
. Materials and Methods
All reactions were carried out under argon atmosphere using gun vacuum dried glassware.
Dry solvents were degassed before the use. All commercial reagents were purchased from Aldrich
Darmstadt, Germany) and TCI (Tokyo Chemica Industry, Tokyo, Japan). Dry solvents were prepared
(
according to standard procedures. Reactions were followed using thin layer chromatography (TLC) on
silica gel-coated plates (Merck 60 F254) with the indicated solvent mixture. Optical rotations were
measured on a Perkin-Elmer 241 MC polarimeter (Vienna, Austria) (c = 1). Column chromatography
was carried out using Merck 60 (40–63 or 230–400 mesh) silica gel. 1H NMR spectra were recorded
at 200 MHz in CDCl3 as solvent. 1H NMR chemical shifts are given in ppm with respect to
tetramethylsilane (TMS) as an internal standard.

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3
.1. (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl-α-d-Glucofuranose (R)-4 [28]
-O-tert-Butyldimethylsilyl-1,2-O-isopropylidene- -d-glucofuranose (3.4 g, 10 mmol) in pyridine
6
α
(
0
10 mL) was treated with freshly distilled thionyl chloride (0.87 mL, 12 mmol). The mixture was kept at
C, and after disappearance of the substrate (24 h) the mixture was poured into water and extracted
◦
with DMC. The extract was dried over MgSO , concentrated in vacuo and separated on silica gel
4
◦
column using n-hexane-diethyl ether (9:1) as an eluent to give (R)-
] = +48.0 (c = 1.4 CH Cl ), H NMR (CDCl ):
4
(1.5 g, 45%), m.p. = 54–56 C,
1
[α
δ
= 6.01 (d, 1H, J = 3.8 Hz, H-1); 4.94 (d, 1H, J = 2.6 Hz,
D
2
2
3
H-3); 4.68 (d, 1H, J = 3.8 Hz, H-2); 4.46 (t, 1H, J = 2.6, 5.5 Hz, H-4); 4.30 (m, 1H, J = 4.8, 5.5, 8.0 Hz, H-5);
4
.12 (dd, 1H, J = 8.0, 10.8 Hz, H-6); 3.93 (dd, 1H, J = 4.8, 10,8 Hz, H-6); 1.50, 1.35 (2s, 6H, 2
×
CH ); 0.89
3
(s, 9H, t-Bu); 0.08 (s, 6H, 2×CH3).
3
.2. (S)-1,2-O-Isopropylidene-(5-O-α-d-glucofuranosyl) t-Butanesulfinate (-)-(S)-10
1 mmol, 0.226 g) of (R)-
◦
(
4
in 10 mL of a solvent (THF, Et O or benzene) was cooled to 0 C and
2
treated with excess of t-butylmagnesium chloride (3 mmol). The progress of the reaction was monitored
with TLC. After 4 h for Et O and THF as the solvents (and 6 h for benzene as a solvent), the mixture was
2
worked up with 10 mL of saturated ammonium chloride and extracted 3 times with DCM (3
Combined extracts were dried over magnesium sulfate and evaporated. Separated on silica gel column
using DCM: Et O 1:1 as an eluent gave desired product 10: 0.291 g (90% for Et O as a solvent), 0.285 g
×
10 mL).
2
2
◦
(
(
(
88% for THF as a solvent), and 0.275 g (85% for benzene as a solvent). M.p. = 60–62 C, [
α
] = 57.8
−
D
1
c = 1.0 DCM). H NMR (CDCl ):
δ = 5.95 (d, 1H, J = 3.5 Hz, H-1); 4.56 (d, 1H, J = 3.5 Hz, H-3); 4.41
3
d, 1H, J = 2.2 Hz, H-2); 4.38 (s, 1H, OH); 4.35 (d, 1H, J = 3.6 Hz, H-4); 4.21 (dd, 1H, J = 2.4, 9.7 Hz,
H-5); 4.17 (d.d, 1H, J = 2.4, 7.3 Hz, H-6); 4.06 (dd, 1H, J = 3.4, 8.7 Hz, H-6); 3.99 (d, 1H, J = 3.5 Hz, H-5);
.55, 1.62 (br, s, 1H, OH); 1.50 (s, 3H, OCH ); 1.31 (s, 3H, OCH ); 1.23 (s, 9H, t-Bu). Anal. Calcd. for
1
3
3
C H O S: C, 48.15; H, 7.41; S, 9.87. Found: C, 48.41; H, 7.23; S, 9.99.
13
24
7
3
.3. t-Butyl Methyl Sulfoxide (+)-(R)-11
A solution of (-)-(S)-10 (0,162 g, 0.5 mmol) in 10 mL of diethyl ether was added dropwise to an
etheral solution of methylmagnesium iodide (1 mmol/10 mL) at room temperature. After completion
of the addition, the reaction mixture was stirred for 2 h at room temperature. The reaction was then
quenched with 10 mL saturated ammonium chloride solution. After being stirred for a while, the layers
were separated and the ether phase was extracted twice with water (2
phases, after saturation with sodium chloride, were extracted with dichloromethane (4
The organic solution was dried over magnesium sulfate and evaporated. A crude product was purified
×
10 mL). The combined water
10 mL).
×
on a silica gel column using dichloromethane - ethyl ether (2:1) as eluent affording (-)-(R)-t-butyl
1
methyl sulfoxide 11 (54 mg, 90%) [
1
α
] =
D
−
4.2 (c = 1.0, acetone), 99% e.e.; H NMR (CDCl ): 2.28 (s, 3H);
3
.15 (s, 9H). These data are fully consistent with the literature data [25,28].
3
.4. Reaction of (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl- α-d-Glucofuranose (+)-(R)-4 with
Phenylmagnesium Bromide
◦
A solution of (+)-(R)-4 (0.133 g, 0.5 mmol) in of THF (5 mL) was cooled to 0 C and treated with
a solution of freshly prepared phenylmagnesium bromide (1.5 mmol) in THF (10 mL). The progress
of the reaction was monitored with TLC and after disappearance of the substrate (1.5 h) the
mixture was treated with aqueous, saturated ammonium chloride solution (7 mL) and extracted
with chloroform (4
×
10 mL). The combined organic phase was dried over magnesium sulfate and
evaporated. The residue was separated on a silica gel column using DCM: ethyl acetate 2:1 and, finally,
with ethyl acetate as eluents for diphenyl sulfoxide 9b (88 mg, 89%) m.p. 69–71 C; H NMR (CDCl ):
◦
1
3
δ
= 7.22–7.36 (m, 6H), 7.47–7.62 (m, 4H) (these data are in accordance with literature data [35
and 1,2-O-isopropylidene- -d-glucofuranose 13 (71 mg, 65% [ ] = 11.2 (c = 1.2, H O- this value
is in accordance with literature data [38]). Substrate (+)-(R)-
–37])
α
α
−
D
2
4
was not detected. A similar reaction

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of (+)-(R)-
4 (0.133 g, 0.5 mmol) with p-toluenemagnesium bromide (1.5 mmol) afforded di-p-tolyl
◦
1
sulfoxide 9c (92 mg, 80%) m.p. 92–94 C; H NMR (CDCl ):
δ
= 2.35, 7.25, and 7.52 (AB system,
3
J = 7.2 Hz, 4H) (these data are in accordance with literature data [39]).
3.5. Reaction of (R)-1,2-O-Isopropylidene-3,5-O-Sulfinyl-α-d-Glucofuranose (+)-(R)-4 with
2,4,6-tri-tert-Butylphenylmagnesium Bromide
A solution of (+)-(R)-
4 (0.133 g, 0.5 mmol) in THF (5 mL) was treated with a solution of
2
,4,6-tri-tert-butylphenylmagnesium bromide in THF (1.5 mmol) [40] at room temperature. The progress
of the reaction was monitored with TLC. Stirring was continued for 7 days without observing the
progress of the reaction, sulfite was still observed. After this time, standard work-up with aqueous,
saturated ammonium chloride solution (7 mL) and extraction with DCM (4 7 mL) gave an organic
solution, which was dried over magnesium sulfate and evaporated. The residue was separated on a
4
×
silica gel column using ethyl acetate -DCM (2:1) and finally ethyl acetate for the substrate (+)-(R)-
4
1
(
104 mg, 78%) and 1,3,5-tri-tert-butylbenzene 14 (158 mg, 86%) ( H NMR in accordance with literature
data [41]). 1,2-O-isopropylidene-α-d-glucofuranose 13 (8 mg, 7%) was also isolated.
3
.6. X-ray Crystallography of (S)-1,2-O-Isopropylidene-(5-O-
Crystal and molecular structure of (S)-1,2-O-isopropylidene-(5-O-
t-butanesulfinate (-)-(S)-10 was determined using data collected at 100K with an Oxford Instruments
α
-d-glucofuranosyl)t-Butanesulfinate (-)-(S)-10
α
-d-glucofuranosyl)
KM4 diffractometer using MoK
α
radiation (Oxford, UK) [42]. The lattice constants were refined by
◦
least-squares fit of 17405 reflections collected in the Ø range 3.67–36.14 [43]. A total of 6250 independent
reflections were used to solve the structure by direct methods and to refine it by full matrix least-squares
2
using F [44]. Hydrogen atoms attached to non-carbon atoms were found in a difference Fourier
map and refined isotropically. Hydrogen atoms attached to carbon atoms were placed geometrically
at idealized positions and refined isotropically, except for the H atoms at the C72 carbon in which
Uiso parameters were constrained with their parent atom. Anisotropic thermal parameters were
refined for all nonhydrogen atoms. The Coot and Mercury (Cambridge, UK) programs were used
for model building and structure visualization [45
R = 0.0633 and wR = 0.1440 for 263 refined parameters and 5270 observed reflections. The absolute
1
,
46]. The final refinement yielded the values of
2
structure was determined by the Flack method [47,48], and the Flack parameter was x = –0.11(9).
The calculated parameters for inverted structure, i.e., with assumed opposite (incorrect) chirality, were:
2
R (inv) = 0.0643, wR (inv) = 0.1561, and x(inv) = 1.06(9). Compound crystallizes in the orthorhombic
1
system, space group P2 2 2 , with the unit cell consisting of four monomers. Crystal data and
1
1 1
experimental details are shown in Table S1 (see SI). The absolute configurations at the stereogenic
atoms are S , RC1, RC2, SC3, SC4, RC5
.
S1
Supplementary Materials: Table S1: Crystal data and experimental details for (S)-1,2-O-isopropylidene-
5-O- -D-glucofuranosyl) t-butanesulfinate 10; Table S2: Asymmetry parameters for the two five-membered
rings in the crystal structure of (S)-1,2-O-isopropylidene-(5-O- -D-glucofuranose) t-butanesulfinate 10
CCDC-229829 contains the supplementary crystallographic data for this paper (for (S)-1,2-O-isopropylidene-
5-O- -glucofuranosyl) t-butanesulfinate (S)-10). These data can be obtained free of charge via https:
(
α
α
.
(
α-d
/
/www.ccdc.cam.ac.uk/structures/, or by mail to data_request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44(0)1223-336033.
Author Contributions: Conceptualization, J.D.; Methodology, B.B., J.D., J.B.; Investigation, J.D., J.B., B.B., M.C.;
Resources, J.D., M.C.; Writing—Original Draft Preparation, J.D., J.B., B.B.; Writing—J.D., J.B., B.B.; Supervision,
J.D.; Funding Acquisition, J.D., M.C. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded in part by the National Science Center, grant number UMO-2014/15/B/
ST5/05329 (for J.D.), and the APC was funded by Molecules Journal.
Acknowledgments: We thank Agnieszka D. Filipczak, and Wiesław R. Majzner, from Institute of Technical
Biochemistry, Ł
ód z´ University of Technology, Poland, for data collection and preliminary structure determination.
J.B. also thanks Michał W. Wieczorek, from Ł
ó
d z´ University of Technology, Poland, for his great support
and continuous encouragement. We also want to thank Dorota Krasowska for the final correction of the
manuscript’s graphic.

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Conflicts of Interest: The authors declare no competing financial interest. The sponsors had no role in the design,
execution, interpretation, or writing of the study.
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Sample Availability: Samples of the compound 10 are available from the authors.
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