Catalytic synthesis of D-glucosaminic acid from D-glucosamine on active charcoal-supported Pd-Bi catalysts

Article abstract of DOI:10.1080/07328300600723757

D-Glucosaminic acid (2-amino-2-deoxy-D-gluconic acid), is a component of bacterial lipopolysaccharides, sweetener, condiments, and a chiral synthon. A catalytic oxidation of D-glucosamine to D-glucosaminic acid by molecular oxygen on active charcoal-supported Pd-Bi catalysts is described in good yield. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/07328300600723757

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Catalytic Synthesis of D‐Glucosaminic
Acid from D‐Glucosamine on Active
Charcoal‐Supported Pd‐Bi Catalysts
a
b
Gu Wen‐xiu & Xia Wen‐shui
a
The School of Chemical & Material Engineering, Southern Yangtze
University, Wuxi, Jiangsu, China
b
The School of Food, Southern Yangtze University, Wuxi, Jiangsu, China
Version of record first published: 23 Aug 2006
To cite this article: Gu Wen‐xiu & Xia Wen‐shui (2006): Catalytic Synthesis of D‐Glucosaminic Acid from
D‐Glucosamine on Active Charcoal‐Supported Pd‐Bi Catalysts, Journal of Carbohydrate Chemistry, 25:4,
297-301
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Journal of Carbohydrate Chemistry, 25:297–301, 2006
Copyright # Taylor & Francis Group, LLC
ISSN: 0732-8303 print 1532-2327 online
DOI: 10.1080/07328300600723757
Catalytic Synthesis of
D-Glucosaminic Acid from
D-Glucosamine on Active
Charcoal-Supported Pd-Bi
Catalysts
Gu Wen-xiu
The School of Chemical & Material Engineering, Southern Yangtze University, Wuxi,
Jiangsu, China
Xia Wen-shui
The School of Food, Southern Yangtze University, Wuxi, Jiangsu, China
D-Glucosaminic acid (2-amino-2-deoxy-D-gluconic acid), is a component of bacterial lipo-
polysaccharides, sweetener, condiments, and a chiral synthon. A catalytic oxidation of
D-glucosamine to D-glucosaminic acid by molecular oxygen on active charcoal-supported
Pd-Bi catalysts is described in good yield.
Keywords D-Glucosaminic acid, D-Glucosamine, Pd-Bi/C catalyst, Oxidation
In recent years, research on D-glucosaminic acid has increased because of
1
its industrial, agricultural, food, and medical applications. D-Glucosaminic
2
acid has recently been identified as a promising sweetener and condiment.
It is also a member of the “chiral pool” and has been used as a starting
material for the asymmetric synthesis of various amino acids and several
3
,4
glycosidase inhibitors. In addition, D-glucosaminic acid has recently been
investigated as an unusual component of Rhizobuim leguminosarum lipopoly-
5
saccharide, and its use as a cation coordinating agent has also been widely
Received September 17, 2005; accepted March 28, 2006.
Address correspondence to Gu Wen-xiu, The School of Chemical & Material Engineer-
ing, Southern Yangtze University, Wuxi, Jiangsu 214036, China. E-mail: guwenxiu@
yahoo.com.cn
297

Gu Wen-xiu and Xia Wen-shui
298
6
studied. D-Glucosaminic acid has also been investigated for potential use in
3
the chromatographic separation of charged biomolecules and as a complex
7
with platinum for cancer therapy. The platinum(IV)/D-glucosaminic acid
complex has received considerable attention because of lower toxicity and the
possibility of oral administration.
There were a few reports in the literature describing the synthesis of
D-glucosaminic acid. The classical synthesis of D-glucosaminic acid from
8
D-glucosamine involves the use of yellow mercuric oxide as an oxidant,
followed by treatment with hydrogen sulfide. The yields of the procedure
were not consistent and the resulting mercuric sulfide was difficult to
separate from the products, which limited applications of D-glucosaminic
acid in the food and pharmaceutical industries. The other strategy for syn-
9
,10
thesis of D-glucosaminic acid is achieved through enzymatic processes.
Thereinto, D-glucosaminic acid was prepared by air oxidation of D-glucosamine
catalyzed by glucose oxidase, whereas glucose oxidase accepted D-glucosamine
only as a poor substrate, with a maximal catalytic efficiency of 2% as
compared to that on D-glucose. Thus, a better yield of D-glucosaminic acid was
dependent on larger amounts of enzyme and prolonged reaction times (72 h).
We propose here a new, facile, and environmentally safe preparation of
D-glucosaminic acid by use of molecular oxygen as an oxidant and Pd-Bi/C
as a catalyst. The catalytic oxidation presents some additional advantages,
namely (i) high selectivities and mild reaction conditions (oxidation with
molecular oxygen at atmospheric pressure near room temperature); (ii) the
possibility of conducting the oxidation in one step in a single reaction vessel;
(iii) a higher site-time yield per catalyst mass; and (iv) much shorter reaction
time (3 h). Moreover, the catalytic process is environmentally clean since it is
conducted on recyclable catalysts and gives no noxious effluents nor side
products.
CATALYST PREPARATION
The Pd-Bi/C catalysts were prepared by a traditional impregnation and
2
reduction method. The cylindrical active charcoal (MCA-210, 1500 m /g,
coconut shell activated carbon, Ningde Xinsen Chemical Industry Co.,
Ltd, China) support was treated with 10% nitric acid, heated on the
boiling water bath with frequent agitation for 2 to 3 h, filtered, washed
with distilled water, and dried for 5 h at 1208C. The dried active charcoal
(10.0 g) was then suspended in distilled water (100 mL) and kept in a
water bath at 808C with stirring; a solution of PdCl (0.83 g) in 35% hydro-
2
chloric acid was added dropwise; and the mixture stirred for 2 h at 808C.
After addition of 35% aqueous formaldehyde solution (1 mL), PdCl2 was
reduced by the slow addition of 30% sodium hydroxide aqueous solution
to weak alkalinity with stirring overnight. The suspension was filtered,

Catalytic Synthesis of D-Glucosaminic Acid
299
resuspended in distilled water (100 mL), and held at 408C with nitrogen
flow bubbled through for 20 min, and glucose (5.0 g) was then added with
stirring. Subsequently, a solution of BiCl3 (0.74 g) in 35% hydrochloric
acid was added dropwise at 408C with a continuous supply of nitrogen.
After addition, the suspension was stirred for another 2 h, laid overnight,
filtered, washed with water until neutral, and air-dried. The contents of
Pd and Bi of the catalyst obtained herein were 3.04% and 1.74%,
respectively.
OXIDATIVE PROCEDURE
A typical procedure is as follows: D-glucosamine hydrochloride (5.0 g) was dis-
solved in water (200 mL), and the pH was adjusted to 7.0 with 1.00 mol/L
NaOH. Then KHCO3 (2.3 g) and Pd-Bi/C (2.0 g) catalyst were added. A
strong oxygen current was bubbled into the mixture with vigorous agitation
at 308C, and after 6 h, the pH rose to 7.8. The catalyst was separated by
filtration, and the filtrate was adjusted to pH 4.0 with 1.00 mol/L HCl and
concentrated under reduced pressure to about 20 mL. Absolute ethyl alcohol
was then added to the above concentrated solution until crystallization was
Figure 1: Tentative scheme for the mechanism of D-glucosamine hydrochloride oxidation on
Pd-Bi/C catalyst.

Gu Wen-xiu and Xia Wen-shui
300
Figure 2: D-Glucosaminic acid.
complete. After the material stood in a refrigerator for several hours, the
crystals were removed by filtration and washed first with cold 85% alcohol
and then with absolute alcohol. The mother liquor and washings were concen-
trated under reduced pressure to about 20 mL and from this concentrate
another crop of crystals was obtained. The product was recrystallized five
times by dissolving in a small amount of water and then adding absolute
ethyl alcohol. This gave pure D-glucosaminic acid as white needle crystals.
Yield: 70%; m.p. 2608C (dec), [a] -15 (c 4, 2.5% aq HCl); lit: [a] -14 (c 1.64,
D
D
1
2
(
.5% aq HCl). H NMR (500 MHz, D O) 4.56 (d, 1H, J ¼ 4 Hz, H-2), 4.02
2
d, J ¼ 4 Hz, H-3), 3.97 (dd, 1H, J ¼ 3 Hz, 12 Hz, H-6b), 3.90 (s, 1H, H-6a),
1
3
3
.89 (br, 1H, H-5), 3.80 (dd, 1H, J ¼ 6 Hz,12 Hz, H-4). C NMR (500 MHz,
D O) 172.2(C-1), 72.5 (C-3), 70.6 (C-5), 67.1 (C-4), 62.5 (C-6), 58.0 (C-2).
2
35
1
21
Dept 65.4 (C-6). n (cm , KBr) 3299, 2964, 1622, 1583, 1406, 1325, 1112,
035, 933. FAB-MS: m/z 196.0 (M þ 1). Anal. Calcd. for C H NO : C, 36.92;
1
6
13
6
H, 6.71; N, 7.18. Found: C, 36.60; H, 6.71; N, 7.03.
We propose that D-glucosamine oxidation on Pd-Bi/C catalyst proceeds
according to the oxidative dehydrogenation mechanism given in Figure 1,
where bismuth acts as an assistant catalyst, avoiding the overoxidation of
the palladium surface.
1
13
H NMR, C NMR, IR, and FAB-MS confirmed the product D-glucosaminic
acid (Fig. 2).
The catalyst Pd-Bi/C was recycled for eight times, and the catalytic activity
and the conversion yield did not apparently change. The conclusion can be
made that the Pd-Bi/C is a highly active catalyst for the oxidation of
D-glucosamine with molecular oxygen under atmospheric pressure at near
room temperature in near neutral medium. Therefore, the present procedure
may be considered as a more practical procedure for the preparation of
D-glucosaminic acid.
The further study of Pd-Bi/C catalyst is under way.

Catalytic Synthesis of D-Glucosaminic Acid
301
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