A practical access to glucose- and allose-based (5+5) 3- spiropseudonucleosides from a common intermediate

Article abstract of DOI:10.1016/j.carres.2013.04.008

A practical access to glucose-based and allose-based spirooxazolidinones is reported. The synthetic sequence consisting of TEMPO-catalyzed oxidation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, Henry reaction, and reduction provides amino alcohol with allo-configuration on a multigram scale. Alternatively, water elimination from Henry products followed by a rehydration gives an access to diastereomerically pure glucose-based nitro alcohol which upon reduction provides complementary amino alcohol with gluco-configuration. The latter amino alcohols are transformed into spirooxazolidinones (3-spiropseudonucleosides) via their N-Cbz or N-phenylcarbamate derivatives. The title compounds easily undergo N-derivatization and give highly crystalline materials. Two of the newly obtained (5+5) 3-spiropseudonucleosides are characterized by X-ray crystallography.

Full text of DOI:10.1016/j.carres.2013.04.008

Accepted Manuscript
A practical access to glucose- and allose-based (5+5) 3-spiropseudonucleosides
from a common intermediate
Māris Turks, Vitalijs Rodins, Evija Rolava, Pāvels Ostrovskis, Sergey Belyakov
PII:
S0008-6215(13)00136-5
DOI:
http://dx.doi.org/10.1016/j.carres.2013.04.008
CAR 6451
Reference:
To appear in:
Carbohydrate Research
Received Date:
Revised Date:
Accepted Date:
4 March 2013
8 April 2013
9 April 2013
Please cite this article as: Turks, M., Rodins, V., Rolava, E., Ostrovskis, P., Belyakov, S., A practical access to
glucose- and allose-based (5+5) 3-spiropseudonucleosides from a common intermediate, Carbohydrate Research
(2013), doi: http://dx.doi.org/10.1016/j.carres.2013.04.008
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A practical access to glucose- and allose-based (5+5) 3-spiropseudonucleosides from
a common intermediate
Māris Turksa,*, Vitalijs Rodinsa, Evija Rolavaa, Pāvels Ostrovskisa, Sergey Belyakovb
aFaculty of Material Science and Applied Chemistry, Riga Technical University, 14/24 Azenes Str., Riga LV-1007, Latvia
bLatvian Institute of Organic Synthesis, 21 Aizkraukles Str, Riga, LV-1006, Latvia
* Corresponding author. Tel.: +371 67089251; fax: +37167615765.
E-mail address: maris_turks@ktf.rtu.lv (M. T).
Abstract
A practical access to glucose-based and allose-based spirooxazolidinones is reported. The synthetic
sequence consisting of TEMPO-catalyzed oxidation of 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose,
Henry reaction and reduction provides amino alcohol with allo-configuration on a multigram scale.
Alternatively, water elimination from Henry products followed by a rehydration gives an access to
diastereomerically pure glucose-based nitro alcohol which upon reduction provides complementary
amino alcohol with gluco-configuration. The latter amino alcohols are transformed into
spirooxazolidinones (3-spiropseudonucleosides) via their N-Cbz or N-phenylcarbamate derivatives. The
title compounds easily undergo N-derivatization and give highly crystalline materials. Two of the newly
obtained (5+5) 3-spiropseudonucleosides are characterized by X-ray crystallography.
Key words: spiropseudonucleosides, spirooxazolidinones, oxidation of diacetone-α-D-glucose, Henry
reaction, carbamates, N-acyl-oxazolidinones
1. Introduction
Carbohydrate-heterocycle conjugates with spirocyclic junction have raised a particular interest in the last
two decades.1 A crucial moment was the discovery of natural product (+)-hydantocidin (1) which
possesses herbicidal activity (Figure 1).2 Since 1990-ties a range of spiro-glycosides has been prepared.
From medicinal chemistry viewpoint some of the most prominent examples include glycogen
phosphorylase inhibitors.3 Some spiro-glycosides are known as α-glucosidases inhibitors,4 others
possess moderate cytotoxic activities against tumor cells.5 On the other hand, glycosidic spiroketals are

valuable building blocks for natural product synthesis,6 but nitrogen containing spiroglycoheterocycles
act as chiral ligands in transition metal catalyzed transformations.7
Besides the natural and man-made spironucleosides several spiropseudonucleosides have been obtained
as well. The latter term was introduced by Fuentes and co-workers to describe various
spiroglycoheterocycles that possess spirocyclic junction at C-atoms other than glycosidic position.8 In
this context numbers n+m (e.g.: 5+5) are used to describe the ring size of the carbohydrate moiety and
nitrogen containing heterocycle (see, general structure 2, Figure 1). Thus, carbohydrate-nitrogen
heterocycle conjugates with non-glycosidic spiranic junction have been obtained in the series of
oxazolidines,9 hydantoins,10 piperazinediones,11 thiazolidines12 to name but a few. This line of research
has brought also other interesting molecular scaffolds that among other applications exhibit glycosidases
inhibiting activities.13 Nevertheless, the number of reported synthesis for sugars with spiroheterocyclic
motifs at C(3) is relatively smaller than that at C(1).13b In 2009, Fuentes and co-workers reported the
synthesis of 3-spirooxazolidinone 3 with allo-configuration which represents a class of (5+5) 3-
spiropseudonucleosides.8
O
NH
O
O
HO
N
H
HO OH
O
O
O
O
1
O
O
reported
structures
O
O
O
O
HN
O
HN
O
O
O
4
3
O
this
work
O
O
O
X
O
Y
Q
Z
2
Figure 1. Hydantocidine (1) and synthetic spiropseudonucleosides (2-4).
Here, we would like to report a practical gram-scale approach towards 3, its diastereoisomer 4 and their
N-derivatives. The present approach revitalizes the use of the Henry reaction on 1,2:5,6-di-O-
isopropylidene-α-D-glucofuranose (diacetone-α-D-glucose) – derived ketone14 and provides practical
preparative procedures towards several useful intermediates in the realm of 3-nitromethyl- and 3-
aminomethyl-gluco- and allofuranose derivatives.

2. Results and Discussions
The synthesis starts with oxidation of diacetone-α-D-glucose (5). Literature survey shows an extensive
use of chromium (VI)-based oxidizing agents to access the corresponding ketone 6 or its hydrate 7.
Thus, the use of pyridinium dichromate15 pyridinium chlorochromate16 and Collins’ reagent
(CrO3•2C6H5N)17 in the academic labs is well documented. Besides their toxicity, these methods lack the
possibility for an easy up-scale. For example, oxidation of more than thirty grams of 5 with Collin’s
reagent brings to difficulties to control the temperature and mass exchange processes. Other oxidation
systems for diacetone-D-glucose include Swern type conditions17,18 which have also found industrial
applications,19 Dess-Martin periodinane20 and the use of ruthenium catalyzed methods.21
On the other hand, TEMPO-catalyzed alcohol oxidations with sodium hypochlorite are well documented
and extensively used by synthetic organic chemists.22 Nevertheless, to the best of our knowledge there
are only two reports where TEMPO-catalyzed system is used for oxidation of diacetone-D-glucose.23
Also in our case TEMPO-catalyzed bleach oxidation with careful temperature and pH adjustment24
provided an excellent yield of ketone 6 (contains also hydrate 7) on a 100 g scale.25 It was discovered
that 1H-NMR spectrometry was the most reliable way to control the conversion 5→6+7 (Figure 2).26
O
NaOCl, KBr,
O
O
TEMPO
O
O
HO
5
O
O
O
O
O
O
O
O
+
HO
O
O
O
OH
6
7
90%
Scheme 1. TEMPO catalyzed bleach oxidation of diacetone-D-glucose on a hundred gram scale.
Figure 2. A part of 1H-NMR spectrum (300 MHz, CDCl3) of a crude reaction mixture displaying partial
conversion in the reaction 5→6+7.

With ketone/ketone hydrate mixture in the hand we turned to the formation of C-C bond at C(3) of the
hexofuranose via the Henry reaction. It has been known since early 1970ies that Henry reaction on
ketone 6 (6+7→8+9) occurs with reasonably good diastereoselectivity (Scheme 2).14,17 In most of cases
NaOMe, NaOEt or t-BuOK have been used as bases to obtain the corresponding nitromethanate
anion.17,27 Also NaOH is reported as a base in the aforementioned reaction.28 Despite the fact that the
diastereoselectivity of this reaction is mainly substrate-controlled, it is greatly influenced by the choice
of base and reaction temperature.27b A mechanism of epimerization of the resulting nitro alcohols 8 and
9 under the reaction conditions is also proposed.27c In light of the above mentioned facts it is no surprise
that nitromethane addition to ketone 6 is scale-dependent. We have developed a practical approach that
provides tens of grams of both nitro alcohols with excellent diastereomeric purity. In a typical procedure
o
nitromethane is added to a sodium hydroxide solution in methanol between 0 and + 5 C followed by a
methanolic solution of ketone/ketone hydrate mixture at the same temperature (Scheme 2). At the end of
the reaction the resulting mixture is poured into saturated aqueous solution of ammonium sulfate. It was
found that in this way only major diastereoisomer 8 precipitates. Usually the isolated yield of major
isomer 8 (de > 99%) reaches almost 50%. The aqueous phase contains diastereomeric mixture of 8 and 9
and the total yield of process exceeds 80%.
Scheme 2. Large scale Henry reaction on ketone 6.
Next, application of Albrecht-Moffatt dehydration-rehydration procedure produced diastereomerically
pure 9 in a good yield.14 The reaction sequence includes treatment of diastereomeric mixture of
nitroalcohols 8 and 9 with DMSO/Ac2O at ambient temperature to yield the nitromethylene intermediate
10 (84%) (Scheme 3).29 It should be noted that optimization of reaction conditions allowed the use of
only 3 equivalents of Ac2O on a multigram-scale.28 Treatment of 10 with NaOH in water/THF gave

nitroalcohol 9 in 71% yield. To conclude, according to the present synthetic scheme both diastereomeric
nitroalcohols 8 and 9 are available with good isolated yields and excellent de’s.
O
Ac2O,
DMSO
O
O
O
NaOH
8
9
9
, 71%
+
O
10
, 84%
NO2
Scheme 3. Transformation of a mixture of diastereomeric nitro alcohols into gluco-isomer 9.
There have been published several reports dealing with elucidation of absolute configuration of products
8 and 9. Nevertheless, these latter were based on NMR studies at 100 MHz or chemical transformations
coupled with CD spectra analysis.27a In our hands both nitroalcohols 8 and 9 gave X-ray quality single
crystals. These studies provided unambiguous proof of the relative configuration of both isomers after
40 years of their first synthesis (Figure 3).30,31
ORTEP representation
ORTEP representation
of allo-isomer 8
of gluco-isomer 9
Figure 3. ORTEP representation of nitro alcohols 8 and 9.
Nitromoieties of 8 and 9 were reduced by H2 over Pd/C. Reduction occurs already at 10 atm pressure of
hydrogen; however, at large scale optimal pressure of hydrogen was around 30 to 40 atm (Scheme 4).
Alternatively, reduction can be performed with LiAlH4. Pure aminoalcohols 11 and 13 can be obtained
as solids, nevertheless, they can be transformed into corresponding tosylate salts that are highly
crystalline materials.
For oxazolidinone ring closure we have chosen carbamate approach.32 Isomer 11 was transformed into
both, benzyl carbamate 12a and phenyl carbamate 12b. Cyclisation of both carbamates 12a,b occur well
in DMF solution in the presence of NaH.33 In this way oxazolidinone 3 can be produced quantitatively
from Cbz-protected aminoalcohol 12a in 30 min at ambient temperature.

Scheme 4. Synthesis of 3-spiropseudonucleosides from amino alcohols via carbamate approach.
For practical reasons solvent can be changed from DMF to THF. This change prolonged reaction time to
4 h and somewhat diminished the isolated yield (90%) of product 3. On the other hand, phenylcarbamate
12b underwent cyclisation in biphasic CH2Cl2/water system in the presence of NaOH and
benzyltriethylammonium chloride. Under the latter reaction conditions isolated yield of target
oxazolidinone 3 was 80%. The same approach was used to prepare the corresponding diastereoisomers
14a,b. Thus, reduction of 9, followed by benzylcarbamate formation produced intermediate 14a in
quantitative yield after 2 steps. When treated with NaH in THF, benzylcarbamate 14a provided
spirooxazolidinone 4 in 92% yield. Experimentally easier phase transfer conditions for cyclization
required phenylcarbamate 14b. The latter was obtained as described above in 83% isolated yield and
further cyclized to 4 (quant. yield) in system NaOH/H2O/CH2Cl2/BnEt3NCl.
Next, we elaborated conditions for N-derivatization of obtained spiro-oxazolidinones 3 and 4 (Scheme 5,
Table 1). Pretreatment of the latter with NaH in DMF solution followed by appropriate alkylating,
benzylating, allylating, and propargylating reagents produced the corresponding products 15 and 16 in
good isolated yields. Relative configuration of oxazolidinone 15b as a representative example was
unambiguously established by X-ray diffraction analysis.34 Product 15c bearing N-4-bromobutyl group
can in principle undergo further nucleophilic displacements. When oxazolidinone 3 (2 equiv.) was
treated with 1,4-dibromobutane (1 equiv.), dimer 17 was isolated in 18% yield along with product 15c
(Scheme 5).
Oxazolidinone 3 underwent also arylation with Sanger reagent (Table 1, entry 7) and acylation with acyl
chlorides (Table 1, entries 8-10). The molecular structure of N-phenylacetyl derivative 15j was
established by X-ray studies.35

X-ray structures of 15b and 15j reveal similar features: in both compounds furanose cycle adopts
envelope conformations. The spiro atom deviates from the least-square plane by 0.614(5)Å in N-ethyl
derivative 15b and by 0.584(3)Å in N-phenylacetyl derivative 15j. In both structures the oxazolidinone
plane is almost perpendicular to the tetrahydrofuran plane as dihedral angles between two planes equal to
87.0° and 89.1° in compounds 15b and 15j, respectively.
Scheme 5. N-Derivatization of 3-spiropseudonucleosides via alkylation, arylation and acylation.

Table 1. Synthesis of N-derivatized spirooxazolidinones 3→15a-j, 4→16a-g (see Scheme 5)
Entry
RXa
allo-
gluco-
Product 15,
yield
Product 16,
yield
1
2
3
4
5
6
MeI
15a, 90%
15b, 82%
15cb, 82%
15d, 91%
15e, 95%
15f, 89%
16a, 84%
16b, 68%
-
EtBr
Br(CH2)4Br
BnBr
16c, 83%
16d, 88%
16e, 92%
H2C=C(CH3)CH2Br
HC≡CCH2Br
NO2
7
15g, 77%
-
O2N
F
8
AcCl
15h, 71%
15i, 90%
15j, 93%c
-
9
n-PrC(O)Cl
BnC(O)Cl
16f, 96%
16g, 53%c
10
aReaction conditions if not stated otherwise: NaH, DMF
bProduct 15c was isolated as a monomer bearing N-4-bromobutyl group when reagents 3 and Br(CH2)4Br were used 1:4.
cReaction conditions: BuLi, THF
3. Conclusions
In summary, we have developed a practical access to both diastereomeric forms of oxazolidinone-based
(5+5) 3-spiropseudonucleosides and their N-alkyl, aryl, and acyl derivatives. Derivatives 15c, 15e, 15f,
and 15h possess appropriate functionalities for further derivatization. This opens possibilities for
creation of novel types of spiroglycoconjugates via processes like SN2, metathesis, and azide-alkyne
click reactions. The over-all synthetic scheme uses known reactions, albeit stands out with its
practicality, scale-up ability and user friendly approach. Thus, large scale TEMPO catalyzed process
was elaborated for oxidation of diacetone-D-glucose. Additionally, efficient and robust conditions for
convenient synthesis of either of sugars – 1,2:5,6-di-O-isopropylidene-3-C-nitromethyl-α-D-allo-
furanose (8) and 1,2:5,6-di-O-isopropylidene-3-C-nitromethyl-α-D-gluco-furanose (9) on a multigram
scale were developed. Their structures after 40 years were unambiguously assigned by X-ray diffraction
analysis. Starting from one common intermediate, nitro alcohol 8, two 3-C-aminomethyl derivatives 11
and 13 with both allo and gluco configuration can be obtained in an user-friendly manner. In the latter
case dehydration-rehydration sequence inverts the configuration at C(3).
Additionally, both diastereoisomeric spirooxazolidinones can serve as chiral auxiliaries in alkylations of
enolates arising from the corresponding N-acyl derivatives. In this context model compounds 15i,j and
16f,g have shown promising preliminary results that will be reported elsewhere.

4. Experimental section
4.1. General methods
All non-aqueous reactions were carried out under an inert atmosphere of argon in oven-dried glassware
unless otherwise noted. Commercial reagents were used without purification. Solvents were distilled
prior to use and, if required, dried over standard drying agents (THF from metallic sodium, DMSO,
DMF and Et3N form CaH2). Analytical thin layer chromatography (TLC) was performed on Merck
precoated analytical plates, 0.25 mm thick, silica gel 60F254. Preparative flash chromatography was
performed on silica gel (60 Å, 40-63 μm, ROCC). Melting points were recorded with a Fisher Digital
Melting Point Analyzer Model 355 apparatus and are uncorrected. IR spectra were recorded as thin films
on KBr plates or in KBr with FT-IR Perkin Elmer Spectrum BX. Optical rotations were measured at 25
°C on a Anton Paar MCP 500 polarimeter using a sodium lamp as the light source (589 nm). 1H and 13C
NMR spectra were recorded on a Bruker 300 MHz and Varian 400 MHz spectrometers in CDCl3 or
DMSOd6. The proton signals for residual non-deuterated solvents (δ 7.26 for CDCl3 and δ 2.50 for
DMSOd6) and carbon signals (δ 77.1 for CDCl3 and δ 39.5 for DMSOd6) were used as an internal
1
references for H-NMR and 13C-NMR spectra, respectively. Chemical shifts (δ) values are reported in
ppm and coupling constants J in Hz. HRMS spectra (ESI+) were performed using a Q-TOF Micromass
and elemental analyses on a Carlo-Erba EA1108 analyzer. Yields refer to chromatographically and
spectroscopically homogeneous materials.
4.2.
Synthesis of (3R)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (3)
4.2.1. From benzyloxycarbamate 12a
A solution of 12a (1.00 g, 2.36 mmol, 1 equiv) in dry DMF (10 mL) was added to a suspension of NaH
(60% in mineral oil, 0.200 g, 5.00 mmol, 2.1 equiv) in dry DMF (10 mL) under argon atmosphere at 0
ºC. The resulting mixture was stirred at ambient temperature for 30 min, then ethyl acetate (200 mL) and
a saturated aqueous solution of (NH4)2SO4 (50 mL) was added. The organic layer was extracted with
15% aqueous solution of NaCl (10 × 50 mL), dried over Na2SO4, filtered and evaporated under reduced
pressure. The residue was purified by column chromatography (EtOAc) to afford compound 3 (0.74 g,
quant.) as a white solid.
4.2.2. From phenyloxycarbamate 12b
1.02 M solution of NaOH in water (130 mL) and benzyltriethylammonium chloride (0.73 g, 3.2 mmol,
5-mol%) was added to a stirred solution of 12b (25.80 g, 63.1 mmol, 1 equiv.) in CH2Cl2 (100 mL) at 0

ºC. The resulting biphasic reaction mixture was stirred at 0 ºC for 10 min followed by 1 h at ambient
temperature. The phases were separated and the aqueous residue was extracted with EtOAc (6 × 50 mL).
The CH2Cl2 layer was extracted with aq. 2 M NaOH solution (2 × 20 mL) and with brine (5 × 30 mL).
The combined EtOAc layer was washed with aq. 2 M NaOH solution (2 × 25 mL) and with brine (5 ×
20 mL). Both resulting solutions were dried over Na2SO4, filtered and evaporated under reduced
pressure to afford the title compound 3 as a white solid (16.00 g, 80%). Rf=0.28 (CHCl3/EtOH 19:1).
The analytical data of 3 are consistent with those reported earlier.8 Mp: 161-162 °C (EtOAc/Hex).
1
[α]D25=51 (c 0.8, CHCl3) [lit.8: [α]D25=52 (c 0.8, CH2Cl2)]. H-NMR (CDCl3, 300 MHz, ppm) δ: 6.00
3
3
(bs, 1H, H-N), 5.71 (d, 1H, J = 3.5 Hz, H-C(1)), 4.48 (d, 1H, J = 3.5 Hz, H-C(2)), 4.19-4.07 (m, 3H,
2
H-C(4), H-C(5), Ha-C(6)), 4.04-3.97 (m, 1H, Hb-C(6)), 3.88 (d, AB syst., 1H, J = 9.0 Hz, Ha-C(4`)),
2
13
3.26 (d, AB syst., 1H, J = 9.0 Hz, Hb-C(4`)), 1.61, 1.44, 1.36, 1.31 (4s, 12H, (H3C)2C-O-C(1,5)). C-
NMR (C6D6, 75 MHz, ppm) δ: 158.3, 114.3, 110.2, 102.8, 85.4, 83.8, 77.1, 73.7, 68.0, 44.2, 26.7, 26.6,
26.4, 25.2. IR (KBr) ν, cm-1: 3315, 2925, 1770, 1730, 1375, 1265, 1075, 845. Anal. Calcd for
C14H21NO7 (315.32): C 53.33, H 6.71, N 4.44. Found C 53.59, H 6.75, N 4.44.
4.3.
Synthesis of (3S)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-3,5`-
oxazolidin)-2`-one (4)
4.3.1. From benzyloxycarbamate 14a
A solution of 14a (14.65 g, 35.00 mmol, 1 equiv) in dry THF (150 mL) was added to a suspension of
NaH (60% in mineral oil, 1.993 g, 83.00 mmol, 2.4 equiv) in dry THF (100 mL) under argon
atmosphere at 0 ºC. The resulting mixture was stirred at 0 ºC for 10 min followed by 3 h at ambient
temperature. The mixture was poured into a saturated aqueous solution of NH4Cl (300 mL) and THF
was evaporated under reduced pressure. The aqueous residue was extracted with EtOAc (4 × 100 mL).
The combined organic layer was dried over Na2SO4, filtered and evaporated under reduced pressure.
The residue was purified by column chromatography (EtOAc/hexanes 1:5) to afford compound 4 as a
white solid (10.07 g; 92%).
4.3.2. From phenyloxycarbamate 14b
1.02 M solution of NaOH (0.42 g, 10.5 mmol, 2.1 equiv) in water (10 mL) and benzyltriethylammonium
chloride (0.057 g, 0.249 mmol, 5-mol%) was added to a stirred solution of 14b (2.04 g, 4.98 mmol, 1
equiv) in CH2Cl2 (15 mL) at 0 ºC. The resulting biphasic reaction mixture was stirred at 0 ºC for 10 min
followed by 1 h at ambient temperature. The phases were separated and the aqueous residue was
extracted with CH2Cl2 (9 × 3 mL). The combined organic layer was extracted with solution of 2 M

NaOH (3 × 1.5 mL), with saturated aqueous solution of NaCl (3 × 3 mL) and dried over Na2SO4. The
resulting solution was filtered and evaporated under reduced pressure to afford the title compound 4 as
white solid (1.56 g, quantitative). Rf=0.52 (EtOAc/Hex 3:1); Mp: 89-90 ºC (EtOAc/Hex). [α]D25=26 (c
1.0, CHCl3). 1H-NMR (CDCl3, 300 MHz, ppm) δ: 5.91 (d, 1H, 3J = 3.4 Hz, H-C(1)), 5.58 (bs, 1H, H-N-
3
C(3`)), 4.54 (d, 1H, 3J = 3.4 Hz, H-C(2)), 4.37 (ddd, 1H, J = 8.5, 6.4, 5.1 Hz, H-C(5)), 4.14 (dd, AB
syst., 1H, 2J = 8.9 Hz, 3J = 6.4 Hz, Ha-C(6)), 4.02 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 5.1 Hz, Hb-C(6)),
3.89 (d, 1H, 3J = 8.5 Hz, H-C(4)), 3.83 (d, AB syst., 1H, 2J = 9.2 Hz, Ha-C(4`)), 3.77 (d, AB syst., 1H, 2J
= 9.2 Hz, Hb-C(4`)), 1.50, 1.42, 1.34, 1.32 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (C6D6, 75 MHz,
ppm) δ: 157.9, 112.6, 109.8, 105.2, 87.7, 84.3, 81.8, 73.0, 67.7, 41.9, 27.0 (2C), 26.3, 25.2. IR (KBr) ν,
cm-1: 3325, 2990, 2938, 2888, 1771, 1376, 1263, 1218, 1165, 1077, 1011, 959. Anal. Calcd for
C14H21NO7 (315.32): C 53.33, H 6.71, N 4.44. Found C 53.48, H 6.86, N 4.12.
4.4. Large scale oxidation of diacetone-α-D-glucose (process 5→6+7)
In an open-mouth beaker equipped with mechanical stirrer, a solution of NaBr (4.20 g, 0.04 mol, 0.1
equiv) in water (20 mL) was added to a solution of diacetone-α-D-glucose (5) (104 g, 0.4 mol, 1.0 equiv)
in CH2Cl2 (400 mL), followed by TEMPO (0.300 g, 1.9 mmol, 0.5 mol-%). The resulting mixture was
cooled to -5 – -10 oC (internal temperature) and vigorously stirred, and aqueous solution of NaClO (~1.6
mol/L, pH 9.5, 360 mL, 0.58 mol, 1.45 equiv) was added dropwise in 30 minutes while keeping the
o
internal temperature in the range of -10 - 0 C. After addition of the bleach solution, the resulting
reaction mixture was stirred for 5 minutes. The organic layer was separated and washed successively
with solution of KI (1.60 g, 0.01 mol, 2.5 mol-%) in 0.5 M aqueous hydrochloric acid (100 mL), 10%
aqueous solution of Na2S2O3 (100 mL), saturated aqueous solution of NaHCO3 (100 mL), and brine
(100 mL). After drying (Na2SO4), filtration and evaporation under reduced pressure, the crude product
(93.0 g, ~90%) contained a mixture of ketone 6 and ketone hydrate 7 in various proportions with the
former being the major component. The NMR data and other characteristics of products 6 and 7 fully
correspond to those reported earlier (see electronic supporting information)25,36
.
4.5. Synthesis of 3-C-nitromethyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (8) and 3-C-
nitromethyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (9)
Nitromethane (135 mL, 2.5 mol, 5 equiv) was added to a solution of NaOH (40.0 g, 1.00 mol, 2 equiv)
in MeOH (500 mL) at 0 °C and stirred for 30 min. The resulting mixture was added to a solution of
ketone/ketone hydrate 6/7 (130 g, 0.5 mol, 1 equiv) in MeOH (250 mL) at temperature range 0 - 10 °C

and vigorously stirred. The reaction mixture was stirred at ambient temperature for 2 h and then it was
pured into saturated aqueous solution of (NH4)2SO4 (1 L). The resulting white precipitate was filtered,
washed with water (1 L) and dissolved in ethyl acetate (600 mL). The phases were separated and the
organic layer was washed with brine (200 mL), dried over anhydr. Na2SO4, filtered and evaporated
under reduced pressure to afford the title compound 8 (77 g, 48%, de > 99%) as a white solid. NMR data
and other physicochemical data of the product 8 are consistent with those reported earlier (see electronic
supporting information).14,27a
The first filtrate was extracted with CH2Cl2 and the combined organic layer was washed with brine (100
mL), dried over anhydr. Na2SO4, filtered and evaporated under reduced pressure to afford dark yellow
thick oil (60 g) which consists of epimers 8 (35 g) and 9 (22 g) and a trace amount of unreacted starting
materials (6/7). The total yield of major isomer 8 is 112 g, 70% and minor isomer 9 – 22.0 g, 14%. The
mixture of 8 and 9 is used in the next step without additional purification.
Acetic anhydride (12.7 mL, 0.134 mol, 3 equiv) was added to a stirred solution of a diastereomeric
mixture of nitro sugars 8 and 9 (14.3 g, 44.8 mmol, 1 equiv) in dry DMSO (45.45 mL, 0.639 mol, 14
equiv) at ambient temperature. The resulting reaction mixture was stirred at ambient temperature for 68
h and poured under vigorous stirring into a cold acetate buffer solution (24.6 g AcONa in 200 mL H2O
adjusted to pH 7 with AcOH) at 0 °C. The temperature of the mixture during the entire
neutralization/workup procedure (5 min) was kept at 0…10 °C. The resulting mixture was further
neutralized with saturated aqueous (200 mL) solution of NaHCO3 and solid NaHCO3 (3 g) to pH 6
followed by extraction with 15% EtOAc/Hex (3 × 150 mL). The combined organic layer was washed
with brine (6 × 150 mL), dried over anhydr. Na2SO4, and evaporated. The purification of the crude
product (12.6 g) by column chromatography on silica gel (60 g) (cyclohexane (0.5 L) followed by 10%
of EtOAc in cyclohexane) provided 11.3 g (84%). NMR and other physicochemical data of the product
10 are consistent with those reported earlier (see electronic supporting information).14,29
To a solution of nitro-ene derivative 10 (22.95 g, 76.2 mmol, 1 equiv) in THF (75 mL) an aqueous (100
ml) solution of NaOH (3.66 g, 91.4 mmol, 1.2 equiv.) was added at 30 °C. The resulting mixture was
stirred for 30 min and controlled by TLC. The reaction mixture was neutralized by saturated aqueous
(200 mL) solution of (NH4)2SO4 (155 g) till pH 6...7. The phases were separated and the aqueous
residue was extracted with EtOAc (6 × 100 mL). The organic layers were washed with brine (15 × 100
mL), dried over anhydr. Na2SO4, filtered and evaporated under reduced pressure to afford the title
compound 9 which was purified by crystallization (EtOAc/Hex). Yield: 17.18 g (71%). NMR and other

physicochemical data of the product 9 are consistent with those reported earlier (see electronic
supporting information).14,27a
4.6. Synthesis of 3-C-aminomethyl-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (11)
A solution of nitro alcohol 8 (60 g, 0.18 mol, 1 equiv) in MeOH:THF (3:1, 400 mL) was hydrogenated
at 30 atm and 40 °C in the presence of 10% Pd/C (5.9 g) for 17 h. The resulting mixture was filtered
through celite and washed by MeOH (150 mL). The filtrate was evaporated to dryness under reduced
pressure. The crude product 11 (51 g, 99%) is white solid and shows excellent purity and is used in the
next step without additional purification. Rf=0.63 (CH2Cl2/EtOH 1:4, 1% NH3). The analytical data of
11 are consistent with those reported earlier.37 Mp: 122-123 °C (EtOAc/Hex) [lit.37: Mp: 122-123 °C].
[α]D23=24 (c 1, EtOH) [lit.37: [α]D23=25.4 (c 0.06, EtOH)]; 1H-NMR (CDCl3, 300 MHz, ppm): δ 5.78 (d,
1H, 3J = 3.8 Hz, H-C(1)), 4.70 (d, 1H, 3J = 3.8 Hz, H-C(2)), 4.17-4.05 (m, 2H, H-C(5), Ha-C(6)), 3.96-
3.88 (m, 1H, Hb-C(6)), 3.85-3.80 (m, 1H, H-C(4)), 3.30-3.23 (m, 2H, H-C(3`)), 2.19-1.45 (bs, 3H, H2N-
C(3`), HO-C(3)), 1.60, 1.45, 1.37, 1.36 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm)
δ: 112.5, 109.8, 103.6, 81.6, 80.5, 79.5, 73.2, 68.0, 42.6, 26.7, 26.5, 25.3. IR (KBr) ν, cm-1: 3500-3400
(bs), 3370, 2990, 1070, 1010.
4.7. Synthesis of 3-C-(N-Benzyloxycarbonyl)aminomethyl-1,2:5,6-di-O-isopropylidene-α-D-
allofuranose (12a)
Triethylamine (16 mL, 115.1 mmol, 1.5 equiv) was added to a solution of 11 (22.2 g, 76.7 mmol, 1
equiv.) in THF (350 mL). Reaction mixture was cooled to -5 ºC and solution of CbzCl (13.1 mL, 91.8
mmol, 1.2 equiv) was added. The resulting mixture was stirred at ambient temperature for 3 h. Then the
excess of THF was evaporated under reduced pressure and dissolve in ethyl acetate (150 mL) and water
(300 mL). The aqueous residue was extracted with ethyl acetate (3 × 100 mL). The combined organic
layer was washed with saturated aqueous solution of CuSO4 (200 mL), NaHCO3 (200 mL) and NaCl
(150 mL), dried over Na2SO4, filtered and evaporated under reduced pressure. Purification by
crystallization (EtOAc/Hex) yielded 12a (23.4 g, 72%). Rf=0.55 (EtOAc/Tol 1:2); Mp: 117 °C.
1
[α]D23=36 (c 0.38, CHCl3). H-NMR (DMSOd6, 400 MHz, ppm) δ: 7.39-7.29 (m, 3H, H-C(Ph)), 7.20-
7.13 (m, 2H, H-C(Ph)), 5.62 (d, 1H, 3J = 3.9 Hz, H-C(1)), 5.07 (d, AB syst., 1H, 2J = 12.5 Hz, Ha-C(a)),
5.04 (d, AB syst., 1H, 2J = 12.5 Hz, Hb-C(a)), 4.89 (s, 1H, H-N-C(3`)), 4.26 (d, 1H, 3J = 3.9 Hz, H-C(2)),
4.16 (dt, 1H, 3J = 6.2, 6.6 Hz, H-C(5)), 3.96 (dd, 1H, 2J = 7.8 Hz, 3J = 6.6 Hz, Ha-C(6)), 3.85 (d, 1H, 3J =
2
3
6.2 Hz, H-C(4)), 3.70 (dd, 1H, J = 7.8 Hz, J = 6.6 Hz, Hb-C(6)), 3.15 (m, 2H, H-C(3`)), 1.46, 1.33,

1.26, 1.24 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (DMSOd6, 100 MHz, ppm) δ: 157.1, 137.2, 128.5,
128.0, 127.9, 111.6, 108.5, 103.1, 80.5, 79.4, 72.8, 66.1, 65.8, 42.6, 42.4, 26.7, 26.5, 26.4, 25.2. IR
(KBr) ν, cm-1: 3450, 3345, 2990, 1790, 1730, 1545, 1385, 1245, 1075, 1010, 860. Anal. Calcd for
C21H29NO8 (423.46): C 59.56, H 6.90, N 3.31. Found C 59.57, H 6.94, N 3.20.
4.8.
Synthesis of 3-C-(N-Phenyloxycarbonyl)aminomethyl-1,2:5,6-di-O-isopropylidene-α-
D-allofuranose (12b)
Triethylamine (12.8 mL, 92.0 mmol, 1.2 equiv) was added to a stirred solution of 11 (22.3 g, 77.0 mmol,
1 equiv.) in dry THF (500 mL) under argon atmosphere and the resulting mixture was cooled to 0 ºC.
After 10 min phenyl chloroformate (11.0 mL, 85.0 mmol, 1.1 equiv) was added dropwise at 0 ºC. The
resulting reaction mixture was stirred at ambient temperature for 1.5 h. Then it was evaporated to
dryness under reduced pressure and redissolved in ethyl acetate (500 mL) and saturated aqueous solution
of NaCl (500 mL). The phases were separated and the aqueous residue was extracted with EtOAc (4 ×
100 mL). Organic layer was washed with brine (8 × 20 mL), dried over Na2SO4 and evaporated under
reduced pressure. A recrystallisation of crude product from hexane/ethylacetate afforded the title
compound 12b as a white solid (25.8 g, 82%). Rf=0.50 (Tol/EtOAc 1:1); Mp: 125-126 °C (EtOAc/Hex).
1
3
[α]D25=44 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm) δ: 7.37 (t, 2H, J =8.0 Hz, H-C(Ar)), 7.21
(t, 1H, 3J = 8.0 Hz, H-C(Ar)), 7.13 (d, 2H, 3J = 8.0 Hz, H-C(Ar)), 5.80 (d, 1H, 3J = 4.0 Hz, H-C(1)), 5.65
(dd, 1H, 3J = 7.8, 4.5 Hz, H-N-C(3`)), 4.42 (d, 1H, 3J = 4.0 Hz, H-C(2)), 4.17-4.10 (m, 2H, H-C(5), Ha-
C(6)), 3.96-3.89 (m, AB syst., 1H, Hb-C(6)), 3.80 (d, 1H, 3J = 7.9 Hz, H-C(4)), 3.61 (dd, AB syst., 2H,
2J = 14.0 Hz, 3J = 7.8 Hz, Ha-C(3`)), 3.56 ((dd, AB syst., 2H, 2J = 14.0 Hz, 3J = 4.5 Hz, Hb-C(3`)), 2.97
(bs, 1H, HO-C(3)), 1.60, 1.47 (2s, 6H, (H3C)2C-O-C(1,5)), 1.37 (s, 6H, (H3C)2C-O-C(1,5)). 13C-NMR
(CDCl3, 75.5 MHz, ppm) δ: 156.9, 150.9, 129.4, 125.6, 121.5, 112.7, 109.6, 104.6, 86.2, 82.7, 82.4,
72.3, 67.8, 44.2, 27.1, 26.7, 26.5, 25.1. IR (KBr) ν, cm-1: 3365, 2985, 1720, 1530, 1495, 1485, 1385,
1375, 1215, 1070, 1015, 875, 845. Anal. Calcd for C20H27NO8 (409.17): C 58.67, H 6.65, N 3.42. Found
C 58.87, H 6.58, N 3.42.
4.9.
(13)
Synthesis of 3-(S)-3-Aminomethyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
A solution of nitro alcohol 9 (20.72 g, 65.00 mmol, 1 equiv) in ethanol (300 mL) was hydrogenated at
35 atm and 40 °C in the presence of 5% Pd/C (2.10 g) for 14 h. The resulting mixture was filtered
through celite and washed by EtOH (100 mL). The filtrate was evaporated to dryness under reduced

pressure. The crude product 13 (18.54 g, 99%) shows excellent purity and is used in the next step
without additional purification. Rf=0.64 (CH2Cl2/EtOH 1:4, 1% NH3). The analytical data of 13 are
consistent with those reported earlier.37 Mp: 111 ºC (EtOAc/Hex). [α]D25=19 (c 1.0, CHCl3). H-NMR
1
3
3
(CDCl3, 300 MHz, ppm) δ: 5.87 (d, 1H, J = 3.6 Hz, H-C(1)), 4.31 (ddd, 1H, J = 8.1, 6.2, 5.3 Hz, H-
C(5)), 4.30 (d, 1H, 3J = 3.6 Hz, H-C(2)), 4.12 (dd, AB syst., 1H, 2J = 8.7 Hz, 3J = 6.2 Hz, Ha-C(6)), 4.02
2
3
3
(dd, AB syst., 1H, J = 8.7 Hz, J = 5.3 Hz, Hb-C(6)), 3.76 (d, 1H, J = 8.1 Hz, H-C(4)), 3.10 (d, AB
2
2
syst., 1H, J = 13.0 Hz, Ha-C(3`)), 2.93 (d, AB syst., 1H, J = 13.0 Hz, Hb-C(3`)), 2.21 (bs, 3H, H2N-
C(3`), HO-C(3)), 1.50, 1.41, 1.34, 1.31 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm)
δ: 112.3, 109.2, 104.7, 86.4, 82.5, 80.0, 72.5, 67.6, 41.9, 27.1, 26.8, 26.5, 25.3. IR (KBr) ν, cm-1: 3332,
3281, 2986, 1617, 1460, 1382, 1165, 1038, 996, 842. Anal. Calcd for C13H23NO6 (289.32): C 53.97, H
8.01, N 4.84. Found C 53.99, H 8.11, N 4.78.
4.10.
Synthesis of 3-C-(N-Benzyloxycarbonyl)aminomethyl-1,2:5,6-di-O-isopropylidene-α-
D-glucofuranose (14a)
An ice-cold solution of Na2CO3 (4.77 g, 45.00 mmol, 1.3 equiv) in water (200 mL) was added to a
solution of 13 (10.00 g, 34.60 mmol, 1 equiv) in THF (150 mL) at 0 ºC. A solution of CbzOSuc (10.35
g, 42.00 mmol, 1.2 equiv) in THF (150 ml) was added dropwise to the previous mixture at 0 ºC. The
resulting mixture was stirred at 0 ºC for 10 min followed by 2.5 h at ambient temperature. Then the
excess of THF was evaporated under reduced pressure. The aqueous residue was extracted with ethyl
acetate (5 × 50 mL). The combined organic layer was washed with saturated aqueous solution of NaCl
(6 × 20 mL), dried over Na2SO4 and concentrated under reduced pressure. The crude product 14a (14.65
g, quantitative) is used in the next step without purification. Rf=0.52 (EtOAc/Tol 1:1.2); [α]D25=54 (c
1.0, CHCl3). 1H-NMR (CDCl3, 300 MHz, ppm) δ: 7.40-7.32 (m, 5H, H-C(Ph)), 5.85 (d, 1H, 3J = 3.6 Hz,
H-C(1)), 5.47 (t, 1H, 3J = 6.4 Hz, H-N-C(3`)), 5.16 (d, AB syst., 1H, 2J = 12.3 Hz, Ha-C(a)), 5.12 (d, AB
syst., 1H, 2J = 12.3 Hz, Hb-C(a)), 4.36 (d, 1H, 3J = 3.6 Hz, H-C(2)), 4.32 (ddd, 1H, 3J = 8.1, 6.4, 5.3 Hz,
H-C(5)), 4.13 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.4 Hz, Ha-C(6)), 3.99 (dd, AB syst., 1H, 2J = 8.9 Hz,
3J = 5.3 Hz, Hb-C(6)), 3.80 (dd, AB syst., 1H, 2J = 14.9 Hz, 3J = 6.4 Hz, Ha-C(3`)), 3.76 (d, 1H, 3J = 8.1
2
3
Hz, H-C(4)), 3.41 (dd, AB syst., 1H, J = 14.9 Hz, J = 6.4 Hz, Hb-C(3`)), 1.49, 1.41, 1.34, 1.30 (4s,
12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 136.2, 128.8, 128.5, 128.3, 109.7, 104.8,
86.2, 83.0, 82.7, 73.0, 72.6, 67.9, 67.5, 44.3, 27.3, 26.9, 26.6, 25.6, 25.3. IR (KBr) ν, cm-1: 3354, 3033,
2987, 2938, 2890, 1737, 1531, 1455, 1372, 1257, 1165, 1074. HRMS (ESI): m/z Calcd for
C21H29NO8Na ([M+Na]+): 446.1781. Found 446.1791.

4.11.
Synthesis of 3-C-(N-Phenyloxycarbonyl)aminomethyl-1,2:5,6-di-O-isopropylidene-α-
D-glucofuranose (14b)
Triethylamine (1.45 mL, 10.00 mmol, 1.5 equiv.) was added to a stirred solution of 13 (2.00 g, 6.92
mmol, 1 equiv) in dry THF (14 mL) under argon atmosphere and the resulting mixture was cooled to 0
ºC. After 10 min phenyl chloroformate (1.08 mL, 8.30 mmol, 1.2 equiv) was added dropwise at 0 ºC.
The resulting reaction mixture was stirred at 0 ºC for 10 min followed by 1 h at ambient temperature.
Then it was evaporated to dryness under reduced pressure and redissolved in ethyl acetate (30 mL). The
ethyl acetate layer was washed with saturated aqueous solution of CuSO4 (5 × 15 mL), saturated
aqueous solution of NaHCO3 (5 × 20 mL), brine (8 × 20 mL) and dried over Na2SO4 and evaporated
under reduced pressure. A recrystallisation of crude product from hexane/ethylacetate afforded the title
compound 4 as a white solid (2.36 g, 83%). Rf=0.61 (EtOAc/Tol 1:1.5); Mp: 148˚C (EtOAC/Hex).
[α]D25= 65 (c 1.0, CHCl3). 1H-NMR (CDCl3, 300 MHz, ppm): 7.37 (t, 2H, 3J =7.5 Hz, H-C(Ar)), 7.22 (t,
1H, 3J =7.5 Hz, H-C(Ar)), 7.15 (d, 2H, 3J =7.5 Hz, H-C(Ar)), 5.89 (d, 1H, 3J =3.6 Hz, H-C(1)), 5.80 (dd,
1H, 3J = 6.8, 6.0 Hz, H-N-C(3`)), 4.44 (d, 1H, 3J =3.6 Hz, H-C(2)), 4.33 (ddd, 1H, 3J = 6.4, 8.7, 5.3 Hz,
H-C(5)), 4.16 (dd, AB syst., 1H, 2J = 8.7 Hz, 3J = 6.4 Hz, Ha-C(6)), 4.00 (dd, AB syst., 1H, 2J = 8.7 Hz,
3J = 5.3 Hz, Hb-C(6)), 3.84 (dd, AB syst., 1H, 2J = 14.8 Hz, 3J = 6.0 Hz, Ha-C(3`)), 3.81 (d, 1H, 3J = 8.7
Hz, H-C(4)), 3.54 (dd, AB syst., 1H, 2J = 14.8 Hz, 3J = 6.8 Hz, Hb-C(3`)), 3.45 (bs, 1H, HO-C(3)), 1.53,
1.45, 1.35, 1.34 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (DMSOd6), 75 MHz, ppm): 156.9, 150.8, 129.3,
125.6, 121.5, 112.6, 109.6, 104.6, 86.1, 82.6, 82.5, 72.3, 67.8, 44.1, 27.1, 26.7, 26.4, 25.1. IR (KBr) ν,
cm-1: 3416, 3364, 3066, 2989, 2926, 2890, 1740, 1552, 1495, 1384, 1373, 1248, 1213, 1168, 1064,
1018. Anal. Calcd for C20H27NO8 (409.43): C 58.67, H 6.65, N 3.42. Found C 58.59, H 6.64, N 3.29.
4.12.
a base
General procedure A for the N-derivatization of oxazolidinones 3 and 4 with NaH as
A solution of compound 3 or 4 in DMF was added to a stirred suspension of NaH (60% suspension in
mineral oil) in DMF under argon atmosphere at 0 ºC. The resulting reaction mixture stirred for 15 min
and then the corresponding halide was added. The resulting reaction mixture was stirred at 0 ºC for 10
min followed by 1 h at ambient temperature. Then it was treated either with EtOH or MeOH and/or
saturated aqueous solution of NH4Cl. The phases were separated and the aqueous residue was extracted
with EtOAc, brine and dried over Na2SO4, filtered and evaporated under reduced pressure to afford the

N-derivatized compound 15 or 16. Purification was done by column chromatography or by
crystallization.
4.12.1. (3R)-3`-Methyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15a)
Compound 15a was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.065 g, 2.69 mmol, 1.7 equiv) suspension in DMF (5.0 mL),
compound 3 (0.500 g, 1.59 mmol, 1 equiv) in DMF (5.0 mL), CH3I (0.15 mL, 2.38 mmol, 1.5 equiv).
Reaction was quenched by MeOH (2.0 mL) and neutralized by saturated aqueous solution of NH4Cl
(3.0 mL). Purification by crystalization (EtOAc/Hex) yielded 15a (0.471 g, 90%). Rf=0.44
1
(CHCl3/EtOH 19:1); Mp: 117-118 °C (EtOAc/Hex). [α]D25=48 (c 1.0, CHCl3). H-NMR (CDCl3, 300
MHz, ppm) δ: 5.72 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.44 (d, 1H, 3J = 3.6 Hz, H-C(2)), 4.17-4.04 (m, 3H, H-
2
3
C(4), H-C(5), Ha-C(6)), 3.98 (dd, AB syst., 1H, J = 8.7 Hz, J = 3.6 Hz, Hb-C(6)), 3.76 (d, AB syst.,
2
2
1H, J = 9.0 Hz, Ha-C(4`)), 3.23 (d, AB syst., 1H, J = 9.0 Hz, Ha-C(4`)), 2.91 (s, 3H, H-C(a)), 1.60,
1.43, 1.35, 1.31 (4s, 12H, (H3C)2-C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 156.4, 114.3, 110.2,
102.3, 84.0, 82.2, 77.3, 73.9, 68.1, 50.3, 31.0, 26.7, 26.5, 26.4, 25.3. IR (KBr) ν, cm-1: 2990, 1765, 1755,
1445, 1385, 1375, 1215, 1075, 1010, 870, 845, 755. HRMS (ESI): m/z Calcd for C15H25NO7 ([M+H]+):
330.1553. Found 330.1584.
4.12.2. (3R)-3`-Ethyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15b)
Compound 15b was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.095 g, 2.39 mmol, 1.5 equiv) suspension in DMF (5.0 mL),
compound 3 (0.500 g, 1.56 mmol, 1 equiv) in DMF (5.0 mL), C2H5Br (0.13 mL, 1.75 mmol, 1.1 equiv).
Reaction was quenched by MeOH (2.0 mL) and neutralized by saturated aqueous solution of NH4Cl
(3.0 mL). Purification by crystallization (EtOAc/Hex) yielded 15b (0.44 g, 82%). Rf=0.40 (CHCl3/EtOH
1
19:1); Mp: 151-152 °C (EtOAc/Hex). [α]D25=39 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm) δ:
5.72 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.43 (d, 1H, 3J = 3.6 Hz, H-C(2)), 4.17-4.04 (m, 3H, H-C(4), H-C(5),
Ha-C(6)), 3.98 (dd, AB syst., 1H, 2J = 8.7 Hz, 3J = 4.0 Hz, Hb-C(6)), 3.78 (d, AB syst., 1H, 2J = 9.0 Hz,
Ha-C(4`)), 3.38 (dq, AB syst., 1H, 2J = 14.0 Hz, 3J = 7.0 Hz, Ha-C(a)), 3.29 (dq, AB syst., 1H, 2J = 14.0
Hz, 3J = 7.0 Hz, Hb-C(a)), 3.21 (d, AB syst., 1H, 2J = 9.0 Hz, Hb-C(4`)), 1.60, 1.43, 1.35, 1.30 (4s, 12H,
3
(H3C)2-C-O-C(1,5)), 1.17 (t, 3H, J = 7.3 Hz, H-C(b)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 155.8,
114.3, 110.2, 103.0, 84.1, 82.2, 77.6, 73.8, 68.2, 47.4, 38.8, 26.7, 26.5, 26.4, 25.3, 12.2. IR (KBr) ν, cm-

1: 2985, 1760, 1750, 1455, 1385, 1215, 1075, 1055, 1010, 875, 845, 755. HRMS (ESI): m/z Calcd for
C16H26NO7 ([M+H]+): 343.1709. Found 344.1731.
4.12.3. (3R)-3`-(4-Bromobutyl)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-
3,5`-oxazolidin)-2`-one (15c)
Compound 15c was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.11 g, 2.7 mmol, 1.7 equiv) suspension in DMF (5.0 mL),
compound 3 (0.500 g, 1.6 mmol, 1 equiv) in DMF (5.0 mL), Br(CH2)4Br (0.74 mL, 6.4 mmol, 4 equiv).
Purification by column chromatography (EtOAc/Hex 45%) yielded 15c (0.586 g, 82%). Rf=0.31
1
(CHCl3/EtOH 19:1); Mp: 183-185 °C (EtOAc/Hex). [α]D25=30 (c 1.0, CHCl3). H-NMR (CDCl3, 300
MHz, ppm) δ: 5.72 (d, 1H, 3J = 3.4 Hz, H-C(1)), 4.45 (d, 1H, 3J = 3.4 Hz, H-C(2)), 4.17-4.05 (m, 3H, H-
2
3
C(4), H-C(5), Ha-C(6)), 4.00 (dd, AB syst., 1H, J = 7.7 Hz, J = 3.8 Hz, Hb-C(6)), 3.80 (d, AB syst.,
1H, 2J = 9.0 Hz, Ha-C(4`)), 3.46 (t, 2H, 3J = 6.2 Hz, H-C(d)), 3.38 (dt, AB syst., 1H, 2J = 14.1 Hz, 3J =
7.1 Hz, Hz, Ha-C(a)), 3.23 (dt, AB syst., 1H, 2J = 14.1 Hz, 3J = 6.6 Hz, Hb-C(a)), 3.20 (d, AB syst., 1H,
2J = 9.0 Hz, Hb-C(4`)), 2.02-1.83 (m, 2H, H-C(c)), 1.83-1.67 (m, 2H, H-C(b)), 1.61, 1.43, 1.35, 1.31 (4s,
12H, (H3C)2-C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 156.2, 114.3, 110.3, 102.9, 84.2, 82.3,
77.5, 73.8, 68.2, 47.9, 43.1, 33.4, 29.0, 26.7, 26.6, 26.4, 25.5, 25.3. IR (KBr) ν, cm-1: 2985, 2355, 1765,
1450, 1385, 1220, 1075, 1040, 1015, 875, 850, 835, 755. Anal. Calcd for C18H28BrNO7 (449.11): C
48.01, H 6.27, N 3.11. Found C 48.12, H 6.26, N 3.07.
4.12.4. (3R)-3`-Benzyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15d)
Compound 15d was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.02 g, 0.48 mmol, 1.5 equiv) suspension in DMF (1.0 mL),
compound 3 (0.10 g, 0.32 mmol, 1 equiv) in DMF (1.0 mL), benzyl bromide (0.11 mL, 1.75 mmol, 5.5
equiv). Reaction was quenched by MeOH (0.2 mL). Additional purification performed by filtration
through activated carbon (EtOH:EtOAc 1:4) yielded 15d (0.12 g, 91%). Rf=0.47 (CHCl3/EtOH 19:1);
1
Mp: 148-151 °C (EtOAc/Hex). [α]D25=20 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm): 7.39-7.30
(m, 5H, H-C(Ph)), 5.63 (d, 1H, 3J = 3.4 Hz, H-C(1)), 4.54 (d, AB syst., 1H, 2J = 15.4 Hz, Ha-C(a)), 4.38
(d, AB syst., 1H, 2J = 15.4 Hz, Hb-C(a)), 4.36 (d, 1H, 3J = 3.4 Hz, H-C(2)), 4.20 (d, 1H, 3J = 8.9 Hz, H-
2
3
C(4)) 4.08 (dd, AB syst., 1H, J = 8.7 Hz, J = 5.8 Hz, Ha-C(6)), 3.98-3.89 (m, 2H, H-C(5), Hb-C(6)),
3.62 (d, AB syst., 1H, 2J = 9.0 Hz, Ha-C(4`)), 3.04 (d, AB syst., 1H, 2J = 9.2 Hz, Hb-C(4`)), 1.61, 1.46,
1.34, 1.33 (4s, 12H, (H3C)2-C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm): 156.2, 135.4, 128.7, 128.1,
128.0, 114.3, 110.2, 102.9, 84.1, 82.3, 77.4, 73.5, 68.1, 48.4, 47.5, 26.7, 26.5, 26.4, 25.2. IR (KBr) ν,

cm-1: 2990, 2935, 1740, 1455, 1370, 1255, 1215, 1080, 1020, 875, 855, 755, 705. Anal. Calcd for
C21H27NO7 (405.44): C 62.21, H 6.71, N 3.45. Found C 62.60, H 7.03, N 3.16.
4.12.5. (3R)-3`-(2-Methylallyl)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-
3,5`-oxazolidin)-2`-one (15e)
Compound 15e was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.07 g, 1.62 mmol, 1.7 equiv) suspension in DMF (5.0 mL),
compound 3 (0.30 g, 0.95 mmol, 1 equiv) in DMF (3.0 mL), 3-chloro-2-methylpropene (0.16 mL,
1.43 mmol, 1.5 equiv). Reaction was quenched by saturated aqueous solution of NH4Cl (15.0 mL).
Purification by filtration through silica gel (EtOAc 40 mL) yielded 15e (0.340 g, 95%). Rf=0.65
1
3
(CHCl3/EtOH 9:1); [α]D25=20 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm): 5.70 (d, 1H, J = 3.5
Hz, H-C(1)), 4.93 (bs, 2H, H-C(c)), 4.41 (d, 1H, 3J = 3.5 Hz, H-C(2)), 4.14 (d, 1H, 2J = 8.7 Hz, H-C(4)),
4.14 (d, AB syst., 1H, 2J = 8.5 Hz, 3J = 5.7 Hz, Ha-C(6)), 4.06 (ddd, 1H, 3J = 8.7, 5.7, 3.4 Hz, H-C(5)),
4.00 (d, AB syst., 1H, 2J = 8.5 Hz, 3J = 3.4 Hz, Hb-C(6)), 3.89 (d, AB syst., 1H, 2J = 14.9 Hz, Ha-C(a)),
3.72 (d, AB syst., 1H, 3J = 9.4 Hz, Ha-C(4`)), 3.71 (d, AB syst., 1H, 2J = 14.9 Hz, Hb-C(a)), 3.08 (d, AB
3
syst., 1H, J = 9.4 Hz, Hb-C(4`)), 1.74 (s, 3H, H-C(d)), 1.60, 1.43, 1.35, 1.30 (4s, 12H, (H3C)2-C-O-
C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm): 156.2, 139.8, 114.4, 114.1, 110.3, 103.0, 84.3, 82.3, 77.4,
73.8, 68.3, 50.7, 47.8, 26.8, 26.6, 26.5, 25.2, 19.7. IR (KBr) ν, cm-1: 2985, 1760, 1750, 1450, 1375,
1255, 1075, 1020, 905, 880, 850. Anal. Calcd for C18H27NO7 (369.41): C 58.52, H 7.37, N 3.79. Found
C 58.28, H 7.37, N 3.69.
4.12.6. (3R)-3`-Propargyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15f)
Compound 15f was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 1.56 g, 65.0 mmol, 1.7 equiv) suspension in DMF (69.0 mL),
compound 3 (12.0 g, 38.1 mmol, 1 equiv) in DMF (56.0 mL), propargyl bromide (80% solution in
toluene, 6.25 mL, 58.0 mmol 1.5 equiv). Neutralized by saturated aqueous solution of NH4Cl (8.00 mL).
Purification by filtration through silica gel (Tol/EtOAc 13:7) yielded 15f (12.00 g, 89%). Rf=0.52
1
(Tol/EtOAc 0.4:1); Mp: 105-108 °C (EtOAc/Hex). [α]D25=27 (c 1.0, CHCl3). H-NMR (CDCl3, 300
3
3
MHz, ppm): 5.73 (d, 1H, J = 3.5 Hz, H-C(1)), 4.46 (d, 1H, J = 3.5 Hz, H-C(2)), 4.17 (dd, AB syst.,
2
4
3
1H, J = 17.6 Hz, J = 2.5 Hz, Ha-C(a)), 4.14 (d, 1H, J = 8.3 Hz, H-C(4)), 4.17-4.09 (m, 2H, H-C(5),
2
4
2
Ha-C(6)), 4.04 (dd, AB syst., 1H, J = 17.6 Hz, J = 2.5 Hz, Hb-C(a)), 3.97 (dd, AB syst., 1H, J = 8.5
Hz, 3J = 3.6 Hz, Hb-C(6)), 3.85 (d, AB syst., 1H, 2J = 9.2 Hz, Ha-C(4`)), 3.34 (d, AB syst., 1H, 2J = 9.2
4
Hz, Hb-C(4`)), 2.31 (t, 1H, J = 2.4 Hz, H-C(c)), 1.61, 1.42, 1.36, 1.30 (4s, 12H, (H3C)2-C-O-

C(1,5)).13C-NMR (CDCl3, 75 MHz, ppm): 155.7, 114.1, 110.4, 103.3, 84.1, 82.6, 77.8, 77.5, 74.0, 73.2,
68.3, 47.1, 34.0, 26.9, 26.8, 26.6, 25.4. IR (KBr) ν, cm-1: 3315, 2995, 1760, 1450, 1385, 1375, 1255,
1220, 1075, 1015, 880, 855. Anal. Calcd for C17H23NO7 (353.37): C 57.78, H 6.56, N 3.96. Found C
57.71, H 6.55, N 3.77.
4.12.7. (3R)-3`-(2,4-dinitrophenyl)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-
3,5`-oxazolidin)-2`-one (15g)
Compound 15g was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.07 g, 1.62 mmol, 1.7 equiv) suspension in DMF (2.0 mL),
compound 3 (0.30 g, 0.95 mmol, 1 equiv) in DMF (2.0 mL), 2,4-dinitrofluorobenzene (0.18 mL,
1.43 mmol, 1.5 equiv). Reaction was quenched by EtOH (2.0 mL) and Neutralized by saturated aqueous
solution of NH4Cl (3.0 mL). Purification by column chromatography (Tol/EtOAc 40%) yielded 15g
(0.350 g, 77%). Rf=0.38 (CHCl3/EtOH 19:1); Mp: 229-231 °C (EtOAc/Hex). [α]D25=-16 (c 1.0, CHCl3).
1H-NMR (CDCl3, 300 MHz, ppm): 8.83 (d, 1H, 4J = 2.6 Hz, H-C(a)), 8.49 (dd, 1H, 4J = 2.6 Hz, 3J = 8.9
Hz, H-C(b)), 7.81 (d, 1H, 3J = 8.9 Hz, H-C(c)), 5.78 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.64 (d, 1H, 3J = 3.6
2
Hz, H-C(2)), 4.22-4.04 (m, 5H, H-C(4), H-C(5), H-C(6), Ha-C(4`)), 3.85 (d, AB syst., 1H, J = 9.0 Hz,
Hb-C(4`)), 1.65, 1.47, 1.40, 1.31 (4s, 12H, (H3C)2-C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm):
153.1, 145.1, 144.0, 136.7, 127.9, 127.4, 121.6, 114.8, 110.6, 103.0, 83.9, 83.8, 77.2, 73.8, 68.2, 49.5,
26.7, 26.6, 26.5, 25.3. IR (KBr) ν, cm-1: 2985, 2895, 2365, 1755, 1540, 1350, 1090, 1025, 875, 855, 835.
Anal. Calcd for C20H23N3O11 (481.13): C 49.90, H 4.82, N 8.73. Found C 49.65, H 4.67, N 8.46. HRMS
(ESI): m/z Calcd for C20H24N3O11 ([M+H]+): 482.1411. Found 482.1436.
4.12.8. (3R)-3`-Acetyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15h)
Compound 15h was prepared by general procedure A. NaH (60% suspension in mineral oil, 0.07 g,
1.62 mmol, 1.7 equiv) suspension in DMF (2.0 mL), compound 3 (0.30 g, 0.95 mmol, 1 equiv) in DMF
(2.0 mL), Ac2O (0.14 mL, 1.43 mmol, 1.5 equiv). Reaction was quenched by saturated aqueous solution
of NH4Cl (3.5 mL). Purification by column chromatography (EtOAc/Tol 35%) yielded 15h (0.240 g,
71%). Rf=0.45 (CHCl3/EtOH 19:1); [α]D25=13 (c 1.0, CHCl3). 1H-NMR (CDCl3, 400 MHz, ppm) δ: 5.74
(d, 1H, 3J = 3.5 Hz, H-C(1)), 4.45 (d, 1H, 3J = 3.5 Hz, H-C(2)), 4.28 (d, AB syst., 1H, 2J = 11.5 Hz, Ha-
2
3
3
C(4`)), 4.13 (dd, AB syst., 1H, J = 8.6 Hz, J = 5.1 Hz, Ha-C(6)), 4.07 (d, 1H, J = 8.9 Hz, H-C(4)),
4.02 (ddd, 1H, 3J = 9.0, 5.1, 3.5 Hz, H-C(5)), 3.97 (dd, AB syst., 1H, 2J = 8.6 Hz, 3J = 3.5 Hz, Hb-C(6)),
2
3.60 (d, AB syst., 1H, J = 11.5 Hz, Hb-C(4`)), 2.49 (s, 3H, H-C(a)), 1.61, 1.41, 1.36, 1.26 (4s, 12H,

(H3C)2-C-O-C(1,5)). 13C-NMR (CDCl3, 100.6 MHz, ppm) δ: 170.1, 151.8, 114.6, 110.3, 103.0, 83.7,
82.7, 77.2, 73.4, 68.2, 45.8, 26.7, 26.4, 26.4, 25.1, 23.0. IR (film) ν, cm-1: 2990, 2935, 1790, 1715, 1695,
1485, 1455, 1370, 875, 845, 755. HRMS (ESI): m/z Calcd for C16H23NO8Na ([M+Na]+): 380.1321.
Found 380.1313.
4.12.9. (3R)-3`-Butiryl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15i)
Compound 15i was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.194 g, 0.0081 mmol, 1.7 equiv) suspension in DMF (20.0 mL),
compound 3 (1.500 g, 4.76 mmol, 1 equiv) in DMF (15.0 mL), n-butyryl chloride (0.768 ml, 7.14 mmol,
1.5 equiv). Purification by column chromatography (EtOAc/Hex 1:4) yielded 15i (1.658 g, 90%). Rf =
0.58 (EtOAc/Hex 1:1); Mp: 112-113 ºC (EtOAc/Hex). [α]D25=12 (c 1.0, CHCl3). 1H-NMR (CDCl3, 300
3
3
MHz, ppm) δ: 5.74 (d, 1H, J = 3.6 Hz, H-C(1)), 4.45 (d, 1H, J = 3.6 Hz, H-C(2)), 4.28 (d, AB syst.,
2
2
1H, J = 11.8 Hz, Ha-C(4`)), 4.16-3.96 (m, 4H, H-C(4), H-C(5), H-C(6)), 3.60 (d, AB syst., 1H, J =
11.8 Hz, Hb-C(4`)), 2.89 (dt, AB syst. 1H, 2J = 16.5 Hz, 3J = 7.4 Hz Ha-C(b)), 2.83 (dt, AB syst. 1H, 2J =
3
3
16.5 Hz, J = 7.4 Hz, Hb-C(b)), 1.69 (sextet, 2H, J = 7.4 Hz, H-C(c)), 1.61, 1.41, 1.36, 1.25 (4s, 12H,
(H3C)2C-O-C(1,5)), 0.97 (t, 3H, 3J = 7.4 Hz, H-C(d)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 173.2, 151.6,
114.7, 110.4, 102.3, 83.8, 82.6, 77.0, 73.4, 68.2, 45.9, 36.9, 26.7, 26.5, 26.4, 25.1, 17.7, 13.7. IR (KBr)
ν, cm-1: 2991, 2965, 2936, 2898, 2878, 1790, 1716, 1381, 1321, 1222, 1076, 1039, 1019. Anal. Calcd
for C18H27NO8 (385.41): C 56.09, H 7.06, N 3.63. Found C 56.16, H 7.11, N 3.60.
4.13.
General procedure B for N-acylation of oxazolidinones 3 and 4 with BuLi as a base
2.5 M n-BuLi in hexanes was added to a cold solution of compound 3 or 4 in dry THF under argon
atmosphere at -78 ºC, stirred for 15 min and then acyl chloride was added. The resulting reaction
mixture was stirred for 1 h at -78 ºC followed by 2 h at ambient temperature. The reaction mixture was
treated with saturated aqueous solution of NH4Cl. The phases were separated and the aqueous residue
was extracted with EtOAc, brine and dried over Na2SO4, filtered and evaporated under reduced pressure
to afford compounds 15j or 16g. Purification was done by column chromatography.
4.13.1. (3R)-3`-Phenylacetyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-
oxazolidin)-2`-one (15j)
Compound 15j was prepared by general procedure B. The following amounts of reagents were used:
Compound 3 (0.050 g, 0.16 mmol, 1 equiv) in THF (2.0 mL), 2.5 M n-BuLi (0.067 ml, 0.17 mmol, 1.05
equiv), phenylacetyl chloride (0.025 ml, 0.19 mmol, 1.2 equiv). Purification by column chromatography

(EtOAc/Hex 1:4) yielded 15j (0.064 g, 93%). Rf=0.63 (EtOAc/Hex 1:1); Mp: 60 ºC (EtOAc/Hex).
1
[α]D25=12 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm) δ: 7.35-7.28 (m, 5H, H-C(Ph)), 5.74 (d,
3
3
2
1H, J = 3.6 Hz, H-C(1)), 4.44 (d, 1H, J = 3.6 Hz, H-C(2)), 4.30 (d, AB syst., 1H, J = 11.7 Hz, Ha-
2
C(4`)), 4.26 (s, 2H, H-C(b)), 4.15-3.97 (m, 4H, H-C(4), H-C(5), H-C(6)), 3.62 (d, AB syst., 1H, J =
11.7 Hz, Hb-C(4`)), 1.63, 1.40, 1.36, 1.20 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz,
ppm) δ: 171.0, 151.6, 133.3, 129.7, 128.5, 127.2, 114.7, 110.4, 103.0, 83.8, 82.6, 77.3, 73.5, 68.2, 46.1,
40.9, 26.7, 26.4, 26.3, 25.0. IR (KBr) ν, cm-1: 3065, 3033, 2991, 2939, 2897, 1789, 1686, 1473, 1456,
1382, 1323, 1227, 1127, 1077, 1028. Anal. Calcd for C22H27NO8 (433.45): C 60.96, H 6.28, N 3.23.
Found C 60.95, H 6.10 , N 3.06.
4.14.
(3S)-3`-Methyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-3,5`-
oxazolidin)-2`-one (16a)
Compound 16a was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.032 g, 0.809 mmol, 1.7 equiv) suspension in DMF (1.5 mL),
compound 4 (0.150 g, 0.48 mmol, 1 equiv) in DMF (3.5 mL), CH3I (0.044 ml, 0.71 mmol, 1.5 equiv).
Purification by column chromatography (EtOAc/Hex 1:5) yielded 16a (0.131 g, 84%).
1
Rf=0.50 (EtOAc/Hex 1:1); Mp: 112 ºC (EtOAc/Hex). [α]D25= 40 (c 1.0, CHCl3). H-NMR (CDCl3, 300
MHz, ppm) δ: 5.90 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.50 (d, 1H, 3J = 3.6 Hz, H-C(2)), 4.34 (ddd, 1H, 3J =
8.4, 6.3, 5.1 Hz, H-C(5)), 4.13 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.3 Hz, Ha-C(6)), 4.00 (dd, AB syst.,
1H, 2J = 8.9 Hz, 3J = 5.1 Hz, Ha-C(6)), 3.87 (d, 1H, 3J = 8.4 Hz, H-C(4)), 3.80 (d, AB syst., 1H, 2J = 9.2
Hz, Ha-C(4`)), 3.62 (d, AB syst., 1H, 2J = 9.2 Hz, Hb-C(4`)), 2.89 (s, 3H, H-C(a)), 1.50, 1.41, 1.33, 1.31
(4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 156.5, 112.9, 109.6, 104.8, 84.4,
84.1, 81.6, 72.4, 67.6, 48.2, 30.9, 26.9, 26.8, 26.4, 24.9. IR (KBr) ν, cm-1: 2989, 2965, 2942, 2886, 1759,
1494, 1432, 1378, 1269, 1246, 1219, 1062, 1042. Anal. Calcd for C15H23NO7 (329.35): C 54.70, H 7.04,
N 4.25. Found C 54.64, H 7.07, N 4.17.
4.16.
(3S)-3`-Ethyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-3,5`-
oxazolidin)-2`-one (16b)
Compound 16b was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.032 g, 1.35 mmol, 1.7 equiv) suspension in DMF (2.5 mL),
compound 4 (0.25 g, 0.79 mmol, 1 equiv) in DMF (2.5 mL), C2H5Br (0.09 ml, 1.19 mmol, 1.5 equiv).
Purification by column chromatography (EtOAc/Hex 1:4) yielded 16b (0.184 g, 68%). Rf=0.43
(EtOAc/Hex 1:1); Mp: 122-123 ºC (EtOAc/Hex). [α]D25=46 (c 1.0, CHCl3). 1H-NMR (CDCl3, 300 MHz,

3
3
3
ppm) δ: 5.89 (d, 1H, J = 3.6 Hz, H-C(1)), 4.49 (d, 1H, J = 3.6 Hz, H-C(2)), 4.32 (ddd, 1H, J = 8.5,
6.3, 5.2 Hz, H-C(5)), 4.13 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.3 Hz, Ha-C(6)), 4.00 (dd, AB syst., 1H,
2J = 8.9 Hz, 3J = 5.2 Hz, Ha-C(6)), 3.86 (d, 1H, 3J = 8.5 Hz, H-C(4)), 3.76 (d, AB syst., 1H, 2J = 9.2 Hz,
2
2
3
Ha-C(4`)), 3.66 (d, AB syst., 1H, J = 9.2 Hz, Hb-C(4`)), 3.37 (dq, AB syst., 1H, J = 14.0 Hz, J = 7.0
2
3
Hz, Ha-C(a)), 3.26 (dq, AB syst., 1H, J = 14.0 Hz, J = 7.0 Hz, Hb-C(a)), 1.49, 1.40, 1.32, 1.29 (4s,
12H, (H3C)2C-O-C(1,5)), 1.15 (t, 3H, 3J = 7.4 Hz, H-C(b)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 156.1,
113.0, 109.7, 104.9, 84.5, 84.3, 82.0, 72.5, 67.8, 45.5, 38.9, 27.0, 26.7, 26.5, 25.1, 12.4. IR (KBr) ν, cm-
1: 2982, 2936, 2926, 2889, 2562, 1763, 1712, 1383, 1168, 1039, 1018. Anal. Calcd for C16H25NO7
(343.37): C 55.97, H 7.34, N 4.08. Found C 56.02, H 7.36, N 3.97.
4.17.
(3S)-3`-Benzyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-3,5`-
oxazolidin)-2`-one (16c)
Compound 16c was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.011 g, 0.27 mmol, 1.7 equiv) suspension in DMF (0.4 mL),
compound 4 (0.050 g, 0.16 mmol, 1 equiv) in DMF (0.5 mL), benzyl bromide (0.028 ml, 0.24 mmol, 1.5
equiv). Purification by crystallization (Hex) yielded 16c (0.053 g, 83%). Rf=0.64 (EtOAc/Hex 1:1); Mp:
1
112 ºC (EtOAc/Hex). [α]D25=38 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz, ppm): 7.39-7.27 (m, 5H,
H-C(Ph)), 5.90 (d, 1H, 3J = 3.6 Hz, H-C(1)), 5.66 (d, AB syst., 1H, 2J = 15.1 Hz, Ha-C(a)), 4.51 (d, 1H,
3J = 3.6 Hz, H-C(2)), 4.33 (ddd, 1H, 3J = 8.7, 6.3, 4.9 Hz, H-C(5)), 4.23 (d, AB syst., 1H, 2J = 15.1 Hz,
Hb-C(a)), 4.11 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.3 Hz, Ha-C(6)), 3.96 (dd, AB syst., 1H, 2J = 8.9 Hz,
3J = 4.9 Hz, Hb-C(6)), 3.80 (d, 1H, 3J = 8.7 Hz, H-C(4)), 3.66 (d, AB syst., 1H, 2J = 9.2 Hz, Ha-C(4`)),
2
13
3.57 (d, AB syst., 1H, J = 9.2 Hz, Hb-C(4`)), 1.46, 1.32, 1.27, 1.16 (4s, 12H, (H3C)2C-O-C(1,5)). C-
NMR (CDCl3, 75 MHz, ppm): 156.5, 135.4, 128.8, 128.3, 128.0, 113.0, 109.8, 104.9, 84.7, 84.4, 81.5,
72.5, 67.9, 48.4, 45.7, 27.0, 26.6, 26.5, 25.1. IR (KBr) ν, cm-1: 3034, 2988, 2935, 2886, 1764, 1494,
1448, 1374, 1265, 1231, 1083, 1057, 1015. Anal. Calcd for C21H27NO7 (405.44): C 62.21, H 6.71, N
3.45. Found C 62.20, H 6.70, N 3.41.
4.18.
(3S)-3`-(2-Methylallyl)-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-
glucofuranose-3,5`-oxazolidin)-2`-one (16d)
Compound 16d was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.026 g, 1.08 mmol, 1.7 equiv) suspension in DMF (3.00 mL),
compound 4 (0.200 g, 0.64 mmol, 1 equiv) in DMF (2.50 mL), 3-chloro-2-methylpropene (0.104 ml,

0.95 mmol, 1.5 equiv). Purification by crystalization (EtOAc/Hex) yielded 16d (0.207 g, 88%). Rf=0.63
1
(EtOAc/Hex 1:1.5); Mp: 114-115 ºC (EtOAc/Hex). [α]D25=56 (c 1.0, CHCl3). H-NMR (CDCl3, 300
MHz, ppm): 5.91 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.93 (s, 2H, H-C(c)), 4.51 (d, 1H, 3J = 3.6 Hz, H-C(2)),
4.38 (ddd, 1H, 3J = 8.8, 6.2, 5.2 Hz, H-C(5)), 4.15 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.2 Hz, Ha-C(6)),
2
3
2
4.00 (dd, AB syst., 1H, J = 8.9 Hz, J = 5.2 Hz, Hb-C(6)), 3.93 (d, AB syst., 1H, J = 15.1 Hz, Ha-
C(4`)), 3.86 (d, 1H, 3J = 8.8 Hz, H-C(4)), 3.67 (d, AB syst., 1H, 2J = 15.1 Hz, Hb-C(4`)), 3.66 (s, 2H, H-
C(a)), 1.75 (s, 3H, H-C(d)), 1.50, 1.40, 1.34, 1.31 (4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75
MHz, ppm): 156.4, 139.5, 113.9, 113.0, 109.8, 104.8, 84.6, 84.3, 81.5, 72.4, 67.7, 50.5, 45.7, 26.9, 26.8,
26.4, 25.0, 19.7. IR (KBr) ν, cm-1: 2991, 2941, 2881, 1760, 1490, 1450, 1374, 1264, 1222, 1078, 1059,
1015, 1001. Anal. Calcd for C18H27NO7 (369.41): C 58.52, H 7.37, N 3.79. Found C 58.59, H 7.38, N
3.76.
4.19.
(3S)-3`-Propargyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-
3,5`-oxazolidin)-2`-one (16e)
Compound 16e was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.044 g, 1.11 mmol, 1.7 equiv) suspension in DMF (3.5 mL),
compound 4 (0.205 g, 0.65 mmol, 1 equiv) in DMF (3.5 mL), propargyl bromide (80% solution in
toluene, 0.11 mL, 0.98 mmol, 1.5 equiv). Purification by column chromatography (EtOAc/Hex 1:3)
yielded 16e (0.210 g, 92%). Rf=0.50 (EtOAc/Hex 3:1); Mp: 122 ºC (EtOAc/Hex). [α]D25=55 (c 1.0,
CHCl3). 1H-NMR (CDCl3, 300 MHz, ppm): 5.91 (d, 1H, 3J = 3.6 Hz, H-C(1)), 4.52 (d, 1H, 3J = 3.6 Hz,
H-C(2)), 4.32 (ddd, 1H, 3J = 8.3, 6.4, 5.1 Hz, H-C(5)), 4.14 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 6.4 Hz,
Ha-C(6)), 4.10 (d, 2H, 4J = 2.6 Hz, H-C(a)), 4.00 (dd, AB syst., 1H, 2J = 8.9 Hz, 3J = 5.1 Hz, Hb-C(6)),
3.90 (d, 1H, 3J = 8.3 Hz, H-C(4)), 3.89 (d, AB syst., 1H, 2J = 9.2 Hz, Ha-C(4`)), 3.78 (d, AB syst., 1H, 2J
4
= 9.2 Hz, Hb-C(4`)), 2.31 (t, 1H, J = 2.6 Hz, H-C(c)), 1.51, 1.42, 1.34, 1.31 (4s, 12H, (H3C)2C-O-
C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm): 155.7, 113.0, 109.7, 104.8, 85.0, 84.1, 81.6, 76.6, 73.4, 72.4,
67.6, 45.5, 33.9, 26.9, 26.8, 26.4, 25.0. IR (KBr) ν, cm-1: 3300, 2995, 2941, 2889, 2126, 1761, 1443,
1259, 1080, 1016. Anal. Calcd for C17H23NO7 (353.37): C 57.78, H 6.56, N 3.96. Found C 57.61, H
6.53, N 3.86.
4.20.
(3S)-3`-Butyryl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-3,5`-
oxazolidin)-2`-one (16f)

Compound 16f was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.130 g, 0.003 mmol, 1.7 equiv) suspension in DMF (8.0 mL),
compound 4 (0.600 g, 0.002 mmol, 1 equiv) in DMF (12.0 mL), butyryl chloride (0.290 ml, 0.003
mmol, 1.5 equiv). Purification by column chromatography (EtOAc/Hex 1:3) yielded 16f (0.701 g, 96%).
Rf=0.48 (Tol/EtOAc 1:5). [α]D25=50 (c 1.0, CHCl3). 1H-NMR (CDCl3, 300 MHz, ppm) δ: 5.92 (d, 1H, 3J
= 3.8 Hz, H-C(1)), 4.53 (d, 1H, 3J = 3.8 Hz, H-C(2)), 4.27 (ddd, 1H, 3J = 8.9, 6.2, 4.5 Hz, H-C(5)), 4.19
(d, AB syst., 1H, 2J = 11.8 Hz, Ha-C(4`)), 4.14 (dd, AB sist., 1H, 2J = 8.9 Hz, 3J = 6.2 Hz, Ha-C(6)), 4.05
2
2
3
(d, AB syst., 1H, J = 11.8 Hz, Hb-C(4`)), 3.99 (dd, AB syst., 1H, J = 8.9 Hz, J = 4.5 Hz, Hb-C(6)),
3
2
3
3.87 (d, 1H, J = 8.9 Hz, H-C(4)), 2.92 (dt, AB syst. 1H, J = 16.6 Hz, J = 7.3 Hz, Ha-C(b)), 2.81 (dt,
2
3
3
AB syst. 1H, J = 16.6 Hz, J = 7.3 Hz, Hb-C(b)), 1.69 (sextet, 2H, J = 7.3 Hz, H-C(c)), 1.50, 1.35,
13
1.33, 1.27 (4s, 12H, (H3C)2C-O-C(1,5)), 0.98 (t, 3H, 3J = 7.3 Hz, H-C(d)). C-NMR (CDCl3, 75 MHz,
ppm) δ: 172.9, 152.1, 113.2, 109.9, 104.7, 85.0, 84.1, 82.0, 72.5, 67.7, 44.8, 37.0, 26.8, 26.7, 26.3, 24.9,
17.7, 13.7. IR (KBr) ν, cm-1: 2986, 2937, 2879, 1790, 1704, 1374, 1258, 1216, 1140, 1060, 1013. HRMS
(ESI): m/z Calcd for C18H28NO8 ([M+H]+): 386.1802. Found 386.1815.
4.21.
(3S)-3`-Phenylacetyl-1,2:5,6-di-O-isopropylidene-spiro(3-deoxy-α-D-glucofuranose-
3,5`-oxazolidin)-2`-one (16g)
Compound 16g was prepared by general procedure B. The following amounts of reagents were used:
compound 4 (0.100 g, 0.32 mmol, 1 equiv) in THF (3 mL), 2.5 M n-BuLi (0.133 ml, 0.33 mmol, 1.05
equiv), phenylacetyl chloride (0.084 ml, 0.63 mmol, 2 equiv). Purification by column chromatography
(EtOAc/Hex 1:10) yielded 16g (0.073 g, 53%). Rf=0.74 (EtOAc/Hex 1:1); [α]D25=28 (c 0.8, CHCl3). 1H-
3
NMR (CDCl3, 300 MHz, ppm) δ: 7.34-7.27 (m, 5H, H-C(Ph)), 5.94 (d, 1H, J = 3.6 Hz, H-C(1)), 4.54
(d, 1H, 3J = 3.6 Hz, H-C(2)), 4.34 (d, AB syst., 1H, 2J = 15.4 Hz, Ha-C(b)), 4.26 (ddd, 1H, 3J = 8.9, 6.2,
4.3 Hz, H-C(5)), 4.22 (d, AB syst., 1H, 2J = 11.8 Hz, Ha-C(4`)), 4.20 (d, AB syst., 1H, 2J = 15.4 Hz, Hb-
2
3
2
C(b)), 4.14 (dd, 1H, J = 8.9 Hz, J = 6.2 Hz, Ha-C(6)), 4.07 (d, AB syst., 1H, J = 11.8 Hz, Hb-C(4`)),
3.99 (dd, 1H, 2J = 8.9 Hz, 3J = 4.3 Hz, Hb-C(6)), 3.88 (d, 1H, 3J = 8.9 Hz, H-C(4)), 1.51, 1.33, 1.27, 1.20
(4s, 12H, (H3C)2C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 170.8, 152.1, 133.5, 129.7, 128.5,
127.2, 113.2, 109.9, 104.8, 85.1, 84.1, 82.2, 75.6, 67.7, 45.1, 41.0, 26.8, 26.5, 26.3, 24.7. IR (KBr) ν,
cm-1: 2989, 2937, 2888, 1797, 1789, 1705, 1372, 1360, 1261, 1165, 1134, 1077, 1017. HRMS (ESI):
m/z Calcd for C22H28NO8 ([M+H]+): 434.1824. Found 434.1815.

14.22. A mixture of (3aR,5R,5'R,6aR)-5-(2,2-Dimethyl-1,3-dioxolan-4-yl)-3'-(4-((3aR,5R,5'R,6aR)-
5-(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyl-2'-oxodihydro-3aH-spiro[furo[2,3-
d][1,3]dioxole-6,5'-oxazolidine]-3'-yl)butyl)-2,2-dimethyldihydro-3aH-spiro[furo[2,3-
d][1,3]dioxole-6,5'-oxazolidin]-2'-one
(17)
and
(3R)-3`-(4-Bromobutyl)-1,2:5,6-di-O-
isopropylidene-spiro(3-deoxy-α-D-allofuranose-3,5`-oxazolidin)-2`-one (15c)
Compound 17 was prepared by general procedure A. The following amounts of reagents were used:
NaH (60% suspension in mineral oil, 0.07 g, 1.62 mmol, 1.7 equiv) suspension in DMF (2.0 mL),
compound 3 (0.30 g, 0.95 mmol, 1 equiv) in DMF (3.0 mL), Br(CH2)4Br (0.06 mL, 1.62 mmol, 0.5
equiv). Reaction was quenched by saturated aqueous solution of NH4Cl (2.00 mL). Purification by
column chromatography (EtOAc/Tol 1:0.3) yielded 17 (0.075 g, 18%) and 15c (0.252 g, 60%). Data for
1
17: Rf=0.25 (CHCl3/EtOH 19:1); Mp: 183-185 °C (EtOAc/Hex). [α]D25=38 (c 0.7, CHCl3). H-NMR
3
3
(CDCl3, 300 MHz, ppm) δ: 5.72 (d, 1H, J = 3.4 Hz, H-C(1)), 4.45 (d, 1H, J = 3.4 Hz, H-C(2)), 4.15
2
3
3
(dd, 1H, J = 8.7 Hz, 3J = 5.5 Hz, Ha-C(6)), 4.14 (d, 1H, J = 8.7 Hz, H-C(4)), 4.07 (ddd, 1H, J = 8.7,
5.5, 3.4 Hz, H-C(5)), 4.01 (dd, 1H, 2J = 8.7 Hz, 3J = 3.4 Hz, Hb-C(6)), 3.74 (d, AB syst., 1H, 2J = 9.2 Hz,
2
Ha-C(4`)), 3.44 (m, 2H, H-C(a)), 3.27 (d, AB syst., 1H, J = 9.2 Hz, Hb-C(4`)), 1.64-1.59 (m, 2H, H-
C(b)), 1.62, 1.44, 1.37, 1.31 (4s, 12H, H3C-C-O-C(1,5)). 13C-NMR (CDCl3, 75 MHz, ppm) δ: 156.3,
114.2, 110.1, 102.9, 84.1, 82.4, 77.4, 73.8, 68.2, 48.1, 43.6, 26.7, 26.5, 26.4, 25.3, 24.1. IR (KBr) ν, cm-
1: 2990, 2940, 2365, 2345, 1755, 1740, 1450, 1375, 1220, 1075, 1015, 875, 850, 755. Anal. Calcd for
[C32H48N2O14·0.5 H2O] (684.31): C 56.13, H 7.07, N 4.09. Found C 55.68, H 7.05, N 4.01.

Acknowledgments
Authors thank the Latvian Council of Science Grant No 10.0030 and Riga Technical University grant
ZP-2012/44 for materials. E.R. thanks ERDF project 2DP/2.1.1.2.0/10/APIA/VIAA/003 for an
opportunity to present this work at 18th European Symposium on Organic Chemistry. Authors thank
JSC “Olainfarm” for kind donation of diacetone-α-D-glucose. E.R. thanks JSC “Olainfarm” and the
Latvian Academy of Sciences for scholarships. Viktors Kumpiņš and Jevgeņija Lugiņina are kindly
acknowledged for helpful discussions.
Supplementary Material
Supplementary data associated with this article can be found in the online version.
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1
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1
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