Chinese Chemical Letters 25 (2014) 1220–1224
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Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
Synthesis of L-glucose and L-galactose derivatives from D-sugars
Tian-Yu Xia, Yang-Bing Li, Zhao-Jun Yin, Xiang-Bao Meng, Shu-Chun Li *, Zhong-Jun Li *
The State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Science, Peking University, Beijing 100191, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 15 April 2014
Received in revised form 3 June 2014
Accepted 3 June 2014
Available online 13 June 2014
An efficient route to prepare L-glucose and L-galactose is described. The L-sugars are achieved by using
the strategy of switching the functional groups at C1 and C5 of D-glucose and D-mannose. The oxidation
and reduction of the silyl enol ether at C1 and the lead(IV) tetraacetate mediated oxidative
decarboxylation at C5 are the key steps. L-Glucose and L-galactose are prepared in a convenient and
inexpensive way.
ß 2014 Shu-Chun Li and Zhong-Jun Li. Published by Elsevier B.V. on behalf of Chinese Chemical
Society. All rights reserved.
Keywords:
Carbohydrates
L-Hexoses
Head-to-tail inversions
Oxidation
Decarboxylation
One-pot procedure
1. Introduction
L-Sugars often have biological activities of medicinal or
agricultural value [1], since they have been found in many
bioactive oligosaccharides, antibiotics, glycopeptides, terpene
glycosides, as well as steroid glycosides and clinically useful
nucleosides. For examples, L-glucose is present in the natural
product, (-)-littoralisone, known as a bioactive agent for increasing
NGF-induced neurite outgrowth in PC12D cells [2]. L-Gulopyranosides are the key constituents of the antitumor drug, Bleomycin
A2 [3] and the nucleoside antibiotic, Adenomycin [4]. The
repeating disaccharide units of heparin [5], heparin sulphate,
and dermatan sulphate glycosaminoglycans contain L-iduronic
acid [6]. Moreover, L-rhamnose and L-mannose are found in the
extracellular polysaccharides S-130, S-88, and S-198 [7], which are
useful in the industry of food and medicine. The phenolic
derivatives of L-mannose that are found in some steroidal
glycosides are potent substrates for measuring the a-L-mannosidase activity of commercial naringinase [8].
Despite extensive application of L-hexoses, it is difficult to
obtain L-hexoses from natural sources. To meet the demands for
L-sugars, it is necessary to develop an efficient method for their
synthesis. In recent years scientists have made great efforts in the
synthetic approaches toward L-pyranosides. They can be classified
into four categories [1], de novo synthesis [9], homologation of
* Corresponding authors.
E-mail addresses: [email protected] (S.-C. Li), [email protected] (Z.-J. Li).
shorter monosaccharides [10], elaboration of D-sugars [11] and
enzymatic synthesis [12].
Here we report an efficient strategy for the synthesis of
L-glucose and L-galactose by using head-to-tail inversion based on
the works reported by Li et al. [13]. This strategy takes advantage of
the latent symmetrical elements that are present in D-sugars to
produce corresponding L-sugars (Scheme 1). Li and co-workers
conceived an approach to L-glucose involving the b-C-glycoside
prepared from the D-glucosyl acetate using Co2(CO)8-catalyzed
silyloxymethylation [13].
Several other works with similar strategies have been
published: Yang et al. [14], and Doboszewski and Herdewijn
[15] had generated L-gulose, L-galactose, L-glucose, and L-allose,
using reduction of the aldehyde functional group at C-1 to a
primary alcohol and oxidation of the C-6 alcohol to an aldehyde
from D-glucose, D-galactose, D-gulose, and D-allose, respectively.
Wei et al. [11d,11f] developed an alternative transformation of
4-deoxypentenosides for the preparation of L-hexoses. And they
also achieved the synthesis of the L-galactose derivative through a
D-glucal intermediate [11e]. Martı́nez et al. [16] have developed an
efficient strategy to convert D-glucose to L-glucose and L-glucuronic
acid by periodate cleavage and regiospecific periodate oxidation of
the C6–C7.
Differing from Li’s work [13] which could give different
orthogonally protected building blocks of L-hexoses containing
oligosaccharides from D-glucose, our strategy could give different
pentaacetate L-sugars from different D-sugars. The strategy of
head-to-tail inversion represents one of the most expedient ways
to prepare L-monosaccharides of high optical purity, and should be
http://dx.doi.org/10.1016/j.cclet.2014.06.007
1001-8417/ß 2014 Shu-Chun Li and Zhong-Jun Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
[(Schem_1)TD$FIG]
T.-Y. Xia et al. / Chinese Chemical Letters 25 (2014) 1220–1224
1221
Scheme 1. Interchange of groups at C1 and C5.
considered particularly suitable for large scale preparation.
Moreover, the strategy can be applied for the assembly of
L-hexoses or other rare sugars in biologically relevant oligosaccharide sequences.
The route we developed for the synthesis of L-glucose and
L-galactose from D-hexoses utilized the strategy to switch the
functional groups at C1 and C5. The strategy was achieved by a
one-pot procedure with the oxidation and reduction of the silyl
enol ether at C1, and the lead(IV) tetraacetate mediated oxidative
decarboxylation at C5. In this case, we achieved a simple and
convenient way to synthesize unnatural L-hexoses from the
naturally abundant D-hexoses.
2. Experimental
2.1. General
All chemicals were purchased as reagent grade and used
without further purification, unless otherwise noted. Dichloromethane was distilled over calcium hydride. THF and toluene were
distilled over sodium. Analytical TLC was performed on silica gel 60
F254 precoated on glass plates, with detection by fluorescence
and/or by staining with 5% concentrated sulfuric acid in EtOH.
Column chromatography was performed on silica gel (230–400
mesh). Optical rotations were measured using a polarimeter at
25 8C. The 1H NMR spectra were recorded using CDCl3, as solvents
at 25 8C. Chemical shifts (in ppm) were referenced with
tetramethylsilane (d 0) in CDCl3. The 13C NMR spectra were
calibrated with CDCl3 (d 77.16). The positions of hydroxyl groups of
mono-ols were determined by the 2D COSY. High-resolution mass
spectrum (HRMS) was obtained using electrospray ionization (ESI)
mass spectroscopy. Air-sensitive reactions were performed in
flame-dried glassware under argon. Organic solvents were
evaporated with a rotary evaporator.
2.1.1. General procedure for preparation of ketone 3
Compound 1 (10 mmol) in water (40 mL) was added sodium
bicarbonate (15 mmol) and pentane-2,4-dione (12 mmol). After
stirring at 90 8C for the given time, the reaction was monitored by
TLC. After completion, the reaction mixture was washed with
CH2Cl2 (50 mL) and treated with Dowex resin (50X8-200, H+ form).
The residue was purified by flash chromatography (CHCl3/
MeOH = 10/1) to give product 2. Compound 2 (45.4 mmol) was
dissolved in dry pyridine (200 mL) and trityl chloride (54.4 mmol)
were added to the solution at 60 8C. After compound 2 disappeared,
acetic anhydride was added to the solution. The solution was
stirred overnight at r.t. and then the reaction was quenched by
addition of MeOH (60 mL) at 0 8C. The solvent was removed
under reduced pressure and the residue was diluted with
CH2Cl2, and successively washed with 1 mol/L HCl(aq),
saturated NaHCO3(aq) and brine. The organic layers were dried
over Na2SO4. After removal of the solvent under reduced pressure,
the residue was purified by flash chromatography (petroleum
ether/EtOAc = 4/1, v/v) to give product 3.
30 -(2,3,4-O-Triacetyl-6-O-trityl-b-D-glucopyranosyl)-20 -propa1
none (3a): ½a25
D +21.5 (c 1.3, CHCl3), yield 85% for 2 steps. H NMR
(400 MHz, CDCl3): d 7.49–7.12 (m, 15H, Ar-H), 5.17 (dt, 2H, J = 18.2,
9.3 Hz, H-3, H-1), 4.95 (t, 1H, J = 9.4 Hz, H-4), 3.96 (td, 1H, J = 9.5,
3.1 Hz, H-2), 3.58–3.51 (m, 1H, H-5), 3.24 (dd, 1H, J = 10.5, 2.1 Hz,
H6a, H6-b), 2.80 (dd, 1H, J = 15.6, 9.2 Hz, –CH2CO–), 2.50 (dd, 1H,
J = 15.6, 3.1 Hz, –CH2CO–), 2.24 (d, 3H, J = 7.8 Hz), 2.03 (s, 3H), 1.98
(s, 3H), 1.72 (s, 3H). 13C NMR (101 MHz, CDCl3): d 205.53, 170.38,
169.91, 169.01, 143.58, 128.69, 127.77, 127.02, 86.46, 74.45, 71.96,
68.74, 61.92, 45.66, 31.32, 20.70, 20.42. HRMS (ESI) Calcd. for
C34H36O9 [M+Na]+: 611.2251; Found: 611.2247.
30 -(2,3,4-O-Triacetyl-6-O-trityl-b-D-mannopyranosyl)-20 -pro1
panone (3b): ½a25
D 8 (c 1, CHCl3), yield 80% for 2 steps. H NMR
(400 MHz, CDCl3): d 7.18–7.5 (m, 15H, Ar-H), 5.33 (dd, 1H,
J = 3.4 Hz, 0.7 Hz, H-3), 5.32 (t, 1H, J = 10.0 Hz, 10.4 Hz, H-2), 5.04
(dd, 1H, J = 10.1, 3.4 Hz, H-4), 4.18 (dd, 1H, J = 8.1, 4.6 Hz, H-1), 3.54
(ddd, 1H, J = 9.9, 4.8, 2.3 Hz, H-5), 3.20 (dd, 1H, J = 10.4, 2.3 Hz,
H-6a), 3.07 (dd, 1H, J = 10.4, 4.9 Hz, H-6b), 2.82 (dd, 1H, J = 16.4,
8.2 Hz, –CH2CO–), 2.47 (d, 1H, J = 4.6 Hz, –CH2CO–), 2.23 (s, 3H),
2.22 (s, 3H), 1.96 (s, 3H), 1.73 (s, 3H). 13C NMR (101 MHz, CDCl3): d
205.01, 170.56, 170.15, 169.23, 143.75, 128.73, 127.74, 126.99,
86.46, 77.84, 73.01, 72.51, 70.27, 66.24, 62.50, 44.48, 30.84, 20.78,
20.66, 20.54. HRMS (ESI) Calcd. for C34H36O9 [M+Na]+ 611.2251;
Found: 611.2249.
2.1.2. General procedure for preparation of heptitol 7
To a solution of ketone 3 (0.26 mmol) in MeCN–cyclohexane
(6:5) (2.2 mL) were added sodium iodide (152 mg), pyridine
(73.4 mL), and then TMSCl (116 mL). The solution was stirred under
argon overnight at 72 8C. The reaction was monitored by TLC. After
compound 3 disappeared, the solvent was removed under reduced
pressure and the residue was diluted with CH2Cl2. Then ozone was
bubbled through the solution for 0.5 h at 78 8C. After compound 4
disappeared, Me2S (0.1 mL) was added and the temperature was
raised to room temperature. The reaction was then diluted with
CH2Cl2 and successively washed with saturated NaHCO3(aq) and
brine. After drying over Na2SO4, NaBH(OAc)3 (276 mg) was added
and stirred until compound 5 disappeared. MeOH (0.1 mL) was
added to quench the reaction and then washed with saturated
NaHCO3(aq) and brine. After drying over Na2SO4, compound 6 was
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T.-Y. Xia et al. / Chinese Chemical Letters 25 (2014) 1220–1224
dissolved in dry pyridine. Acetic anhydride was added to the
solution and then stirred overnight at r.t. The reaction was
quenched by addition of MeOH (1 mL). The residue was purified by
flash chromatography (petroleum ether/EtOAc = 6/1, v/v) to give
product 7 as semisolids.
1,3,4,5-O-Tetraacetyl-7-O-trityl-2,6-anhydro-D-glycero-Dgluco-heptitol (7a): ½a25
D 8 (c 1, CHCl3), yield 54% for 4 steps.
1
H NMR (300 MHz, CDCl3): d 7.43–7.46 (m, 6H, Ar-H), 7.20–7.32
(m, 9H, Ar-H), 5.13–5.18 (m, 3H, H-3, H-4, H-1), 4.27 (d, 2H,
J = 3.5 Hz, –CH2O–), 3.68–3.71 (m, 1H, H-2), 3.56–3.57 (m, 1H, H5), 3.25 (dd, 1H, J = 2.1, 10.2 Hz, H-6a), 3.07 (dd, 1H, J = 4.5, 10.5 Hz,
H-6b), 2.10 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H), 1.73 (s, 3H). 13C NMR
(75 MHz, CDCl3): d 170.88, 170.64, 169.70, 169.11, 143.74, 128.79,
127.85, 127.08, 86.55, 75.65, 74.55, 68.74, 68.63, 62.26, 62.22,
20.66, 20.58, 20.55, 20.30. HRMS (ESI) Calcd. for C34H36O10
[M+Na]+: 627.2201; Found: 627.2188.
1,3,4,5-O-Tetraacetyl-7-O-trityl-2,6-anhydro-D-glycero-Dmanno-heptitol (7b): ½a25
D +8 (c 1, CHCl3), yield 36% for 4 steps.
1
H NMR (400 MHz, CDCl3): d 7.18–7.54 (m, 15H, Ar-H), 5.44 (d, 1H,
J = 2.6 Hz, H-3), 5.31 (t, 1H, J = 10.0 Hz, H-4), 5.00 (dd, 1H, J = 10.1,
3.3 Hz, H-1), 4.27 (dd, 1H, J = 11.2, 6.7 Hz, –CH2O–), 4.12 (m, 1H,
–CH2O–), 3.93 (t, 1H, J = 6.6 Hz, H-2), 3.56 (ddd, 1H, J = 9.9, 4.8,
2.4 Hz, H-5), 3.16 (qd, 2H, J = 10.5, 3.7 Hz, H-6), 2.19 (s, 3H), 2.07 (s,
3H), 1.97 (s, 3H), 1.74 (s, 3H). 13C NMR (101 MHz, CDCl3): d 170.55,
170.38, 170.33, 169.16, 143.75, 128.75, 127.77, 127.01, 86.54,
77.95, 74.04, 72.43, 67.76, 66.21, 62.65, 61.71, 20.77, 20.70, 20.54.
HRMS (ESI) Calcd. for C34H36O10 [M+Na]+: 627.2201; Found:
627.2182.
2.1.3. General procedure for preparation of acid 9
The compound 7 (0.8 mmol) was dissolved in dry MeCN, and
sodium iodide (2.5 mmol) added, and then TMSCl (2.8 mmol) at
0 8C. After compound 7 disappeared, the mixture was diluted with
CH2Cl2 and washed with brine. The organic layer was dried
(Na2SO4), filtered and concentrated to afford compound 8 which
was used without further purification.
To a solution of compound 8 (0.12 mmol) in a mixed solvent of
water and MeCN (1/10 ratio, 3 mL) was consecutively added
2,2,6,6,-tetramethyl-1-piperidinyloxy (0.06 mmol) and iodosobenzene diacetate (0.33 mmol). The reaction was stirred at r.t.
and monitored by TLC. After about 4 h, compound 8 disappeared,
then the solution was diluted with CH2Cl2, and was sequentially
washed with 5% Na2S2O3(aq), saturated KH2PO4(aq). The organic
layer was dried over Na2SO4 and the residue was purified by
column chromatography (trichloromethane/MeOH = 8/1, v/v) to
give product 9.
1,3,4,5-O-Tetraacetyl-2,6-anhydro-D-glycero-D-gluco-hepta1
noic acid (9a): ½a25
D +40 (c 0.4, CHCl3), yield 85% for 2 steps. H NMR
(300 MHz, CDCl3): d 8.30 (s, 1H, –COOH), 5.21–5.32 (m, 2H, H-3, H1), 5.11 (t, 1H, J = 9.9 Hz, H-4), 4.28 (dd, 1H, J = 1.8, 12.3 Hz, –CH2O–
), 4.18 (dd, 1H, J = 12.3 Hz, –CH2O–), 4.07 (d, 1H, J = 9.2 Hz, H-2),
3.75–3.79 (m, 1H, H-5), 2.11 (s, 3H), 2.06 (s, 3H), 2.04 (s, 3H), 2.03
(s, 3H). 13C NMR (75 MHz, CDCl3): d 171.00, 170.42, 170.21, 169.87,
169.57, 75.98, 75.51, 73.29, 68.96, 67.80, 61.85, 20.65, 20.48, 20.45,
[(Schem_2)TD$FIG]
20.41. HRMS (ESI) Calcd. for C15H20O11 [M+Na]+: 399.0898; Found:
399.0888.
1,3,4,5-O-Tetraacetyl-2,6-anhydro-D-glycero-D-manno-hepta1
noic acid (9b): ½a25
D 8 (c 1, CHCl3), yield 70% for 2 steps. H NMR
(400 MHz, CDCl3): d 5.47 (d, 1H, J = 3.0 Hz, H-3), 5.42 (t, 1H,
J = 10.0 Hz, H-4), 5.12 (dd, 1H, J = 3.4, 10.0 Hz, H-1), 4.18 (m, 2H,
H-2,H-5), 4.04 (d, 1H, J = 9.9 Hz, H-6a), 4.00 (t, 1H, J = 6.4 Hz, H-6b),
2.17 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H), 2.01 (s, 3H). 13C NMR
(101 MHz, CDCl3): d 170.48, 170.17, 170.01, 169.90, 74.68, 75.99,
71.40, 67.10, 66.19, 61.54, 20.66, 20.64, 20.62, 20.54. HRMS (ESI)
Calcd. for C15H20O11 [M+Na]+: 399.0897; Found: 399.0901.
2.1.4. General procedure for preparation of pentaacetate L-sugar 10
Compound 9 (1 mmol) was dissolved under argon atmosphere
in a mixture of dry THF (10 mL) and acetic acid (0.1 mL). Lead
tetraacetate (6 mmol) was added to the solution and stirred for
hours (6 h for 9a and 10 h for 9b) and the solid was removed by
filtration. The solution was removed under reduced pressure and
the residue was diluted with CH2Cl2, and washed with 1 mol/L
HCl(aq), saturated NaHCO3(aq) and brine. The organic layers were
dried over Na2SO4 and the solvent was removed under reduced
pressure. The residue was purified by column chromatography
(petroleum ether/EtOAc = 3:1, v/v) to give product 10.
1,2,3,4,6-O-Pentaacetate-L-glucose (10a): Yield 80%. 1H NMR
(400 MHz, CDCl3): d 6.33 (d, 2.16 H, J = 3.7 Hz), 5.72 (d, 1H,
J = 8.3 Hz), 5.47 (t, 2.36 H, J = 9.9 Hz), 5.26 (t, 1H, J = 9.4 Hz),
5.08–5.17 (m, 6.75 H), 4.25–4.31 (m, 3.41 H), 4.08–4.14 (m, 5.91 H),
3.82–3.86 (m, 1H), 2.18, 2.12, 2.10. 2.09, 2.05, 2.04, 2.03, 2.02, 2.02
(9s, 53H). 13C NMR (100 MHz, CDCl3): d 170.58, 170.18, 170.05,
169.61, 169.35, 169.20, 168.91, 168.70, 91.68, 89.04, 72.76, 72.70,
70.21, 69.80, 69.17, 67.87, 67.74, 61.43, 20.83, 20.77, 20.65, 20.62,
20.52, 20.40. HRMS (ESI) Calcd. for C16H22O11 [M+Na]+: 413.1054;
Found: 413.1061.
1,2,3,4,6-O-Pentaacetate-L-galactose (10b): ½a25
16 (c 1,
D
CHCl3), yield 76%. 1H NMR (400 MHz, CDCl3): d 6.38 (d, 1H,
J = 1.5 Hz, H-1), 5.50 (d, 1H, J = 1.3 Hz, H-3), 5.38–5.29 (m, 2H, H-2,
H-5), 4.35 (td, 1H, J = 6.6, 0.9 Hz, H-4), 4.16–4.03 (m, 2H, H-6), 2.16
(d, 6H, J = 0.6 Hz), 2.05 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H). 13C NMR
(101 MHz, CDCl3): d 170.31, 170.09, 170.08, 169.82, 168.86, 89.75,
68.78, 67.45, 67.39, 66.47, 20.84, 20.61, 20.60, 20.56, 20.50. HRMS
(ESI) Calcd. for C16H22O11 [M+Na]+: 413.1054; Found: 413.1055.
3. Results and discussion
In our study, we followed the strategy of Li [13] to elongate and
shorten the carbon chain at C1 and C5, respectively. There are two
key steps in switching the functional groups at C1 and C5. The
strategy of head-to-tail inversion has been achieved.
To elongate the carbon chain and introduce a hydroxylmethyl
group at C1, a methylene ketone was first synthesized. And then
ozone oxidation and followed reduction were used to shorten the
carbon chain to a proper length. The details of synthesis are as
follows (Scheme 2): The formation of compound 2 was from the
initial condensation of the carbanion of the b-diketone with the
Scheme 2. Synthesis of ketone 3 from D-sugar 1. Reagents and conditions: (I) pentane-2,4-dione, NaHCO3, H2O; (II) Py, TrCl, Ac2O, 85% for 3a, 80% for 3b for 2 steps.
[(Schem_3)TD$FIG]
T.-Y. Xia et al. / Chinese Chemical Letters 25 (2014) 1220–1224
1223
Scheme 3. Synthesis of C-glucoside derivative 7. Reagents and conditions: (I) TMSCl, NaI, Py, CH3CN-pentane (6/5), (II) O3, Me2S, 788C; (III) NaBH(OAc)3; (IV) Py, Ac2O, 54%
for 7a, 36% for 7b for 4 steps.
[(Schem_4)TD$FIG]
Scheme 4. Synthesis of acid 9. Reagents and conditions: (I) TMSCl, NaI, CH3CN; (II) TEMPO, DIB, CH3CN-H2O, 85% for 9a, 70% for 9b for 2 steps.
[(Schem_5)TD$FIG]
Scheme 5. Synthesis of L-sugar derivative 10. Reagents and conditions: (I) Pb(OAc)4, THF–AcOH (10/1), 80% for 10a, 76% for 10b.
starting sugar 1, reported by Lubineau et al. [17]. Then, the other
hydroxyl groups were protected, including a trityl group introduced to the hydroxyl group at C6 of 2 with trityl chloride, and
acetylation of the remaining hydroxyl groups (without purification). Compound 3 was obtained in high overall yields.
With ketones 3 in hand, silyl enol ethers were synthesized in
order to introduce the hydroxymethyl groups at C-1 by 4 steps
(Scheme 3). The reactions were carried out by using the Me3SiClNaI-pyridine reagents in MeCN-pentane as described by Norsikian
[18], which was performed at 72 8C for 12 h with good stereoselectivity. Once obtained, the resulting silyl enol ethers 4 were
engaged in an oxidation reaction with ozone at 78 8C in CH2Cl2
for 0.5 h. Under these conditions, the aldehydes 5 were obtained,
reduced by sodium triacetoxyborohydride, and acetylated to form
compounds 7. The elongation at C1 was achieved by this
procedure. Since compound 4 was unstable and compound 5
proved difficult to separate, we turned (or proceeded) to a one-pot
method to carry out all four steps from compound 3 to compound
7. The one-pot procedure achieved a high yield and the operation
was extremely simplified.
We then switched the methylol group to a hydroxyl group at
C5. The subsequent oxidation of primary hydroxyl groups in 8
with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)/iodosobenzene diacetate (DIB) reagent system [18] provided the carboxylic
acid derivatives 9 (Scheme 4). The desired L-sugar derivatives 10
were obtained by oxidative decarboxylation mediated by lead(IV)
tetraacetate [19] (Scheme 5). We found that the compound 10a was
a mixture of a and b configuration, on the contrary, the compound
10b was in major b configuration. We supposed that this result is
due to the different reaction times.
4. Conclusion
In summary, we have developed a new and efficient route for
the synthesis of L-glucose and L-galactose from L-hexoses with the
strategy of head-to-tail inversion in 31% and 15% overall yield. The
strategy was achieved by the oxidation and reduction of the silyl
enol ether at C1, and lead(IV) tetraacetate mediated oxidative
decarboxylation at C5. It was a convenient and inexpensive way to
prepare L-glucose and L-galactose with fewer purification steps,
which will facilitate the preparation of oligosaccharides and
derivatives containing L-glucose and L-galactose.
Acknowledgments
This research was supported by the National Basic Research
Program of China (973 Program, No. 2012CB822100), the National
Key Technology R&D Program ‘‘New Drug Innovation’’ of China
(No. 2012ZX09502001-001) and the National Natural Science
Foundation of China (Nos. 20972012 and 21232002).
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