Aromatic crown ethers as phase transfer catalysts in the synthesis of N-acetylglucosamine β-aryl glycosides

Article abstract of DOI:10.1023/B:RUBI.0000030138.26142.4b

The crown ether-catalyzed glycosylation of phenol, 4-methoxyphenol, and 4-nitrophenol was studied under phase transfer conditions in solid-liquid system. The asymmetric dibenzocrown esters are superior to [3.3]dibenzo-18- crown-6 and 15-crown-5 in the cat

Full text of DOI:10.1023/B:RUBI.0000030138.26142.4b

Russian Journal of Bioorganic Chemistry, Vol. 30, No. 3, 2004, pp. 301–303. Translated from Bioorganicheskaya Khimiya, Vol. 30, No. 3, 2004, pp. 334–336.
Original Russian Text Copyright © 2004 by Chupakhina, Kur’yanov, Chirva, Grigorash, Kotlyar, Kamalov.
LETTERS
TO THE EDITOR
Aromatic Crown Ethers as Phase Transfer Catalysts
in the Synthesis of N-Acetylglucosamine b-Aryl Glycosides
1
T. A. Chupakhina*, V. O. Kur’yanov**, V. Ya. Chirva*, R. Ya. Grigorash**,
S. A. Kotlyar**, and G. L. Kamalov**
Vernadsky Tauric National University, ul. Yaltinskaya 4, Simferopol, 95007 Ukraine
*
*
*Bogatsky Physicochemical Institute, National Academy of Sciences of Ukraine,
Lyustdorfskaya doroga 86, Odessa, 65080 Ukraine
Received November 19, 2003; in final form, January 6, 2004
Abstract—The crown ether-catalyzed glycosylation of phenol, 4-methoxyphenol, and 4-nitrophenol was stud-
ied under phase transfer conditions in solid–liquid system. The asymmetric dibenzocrown esters are superior
to [3.3]dibenzo-18-crown-6 and 15-crown-5 in the catalysis of these reactions.
Key words: aryl glycosides, benzocrown ethers, glycosylation, phase transfer catalysis
We have previously found [1–5] that various phe- ([3.3]DB18C6),
nols are easily glycosylated with 2-acetamido-3,4,6-tri- ([2.4]DB18C6),
[2.4]dibenzo-18-crown-6
[1.5]dibenzo-18-crown-6
O-acetyl-2-deoxy-α-D-glucopyranosyl chloride (I) in ([1.5]DB18C6), and biphenyl-20-crown-6 (BP20C6).
the presence of 15-crown-5 (15C5) under phase trans-
fer conditions (in a solid–liquid system) to give glyco-
sides in 43–86% yields.
The glycosylation was carried out by the procedure
similar to that described in [1] at an aglycon : glycosyl-
donor (I) : K CO : crown ether molar ratio of 1 : 1 : 1 :
2
3
0
.2 in acetonitrile at 25°C. The resulting glycosides
We continued these studies and, with the goal to
reveal a relation between the structure and catalytic
properties of crown ethers, studied the crown ether-cat-
alyzed glycosylation of phenol, 4-methoxyphenol, and
(
V)–(VII) were isolated by column chromatography on
silica gel; their yields and reaction times are shown in
Table 1.
4
-nitrophenol with (I) and catalyzed by various aro-
One can see from Table 1 that the asymmetrical
matic crown ethers (including isomeric ones): benzo- (proximal) aromatic crown esters are as a rule more cat-
1
8-crown-6
(B18C6),
[3.3]dibenzo-18-crown-6 alytically efficient than the symmetrical (distal)
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
B18C6
[3.3]DB18C6
[2.4]DB18C6
O
O
O
O
O
O
O
O
O
O
O
O
[
1.5]DB18C6
BP20C6
1Corresponding author: phone: (0652) 23-3885; e-mail: vladimir@tnu.crimea.ua
068-1620/04/3003-0301 © 2004 MAIK “Nauka /Interperiodica”
1

3
02
CHUPAKHINA et al.
OAc
OH
OAc
R
O
K CO , 15C5
O
AcO
AcO
2
3
AcO
AcO
+
R
O
AcHN
NHAc
(V)–(VII)
Cl
(I)
(II)–(IV)
where (II), (V) R = H, (III), (VI) R = p-NO , (IV), (VII) R = p-OCH .
2
3
Scheme
[
3.3]DB18C6 and 15C5. The highest catalytic activity uct of (I) decomposition in the presence of distal
was found for [1.5]DB18C6, which distinguishes it [3.3]DB18C6 and 15C5.
from the isomeric [3.3]DB18C6 and [2.4]DB18C6.
Our data help state for the first time that the mutual
arrangement of benzene rings in dibenzocrown ether
The catalytic properties of hexadentate macrocycle
BP20C6 are only slightly lower than those of
[
1.5]DB18C6. It was found that only β-glycosides were molecules essentially affect their catalytic properties in
formed in this reaction (Table 2).
the phase transfer reaction of phenol glycosylation.
This enables the design of new efficient complexones
on the basis of crown ethers derived from biphenyl and
Only insignificant amounts of the products of (I)
decomposition were detected by TLC on Sorbfil-AFV-
UV (Sorbpolymer, Russia) at the catalysis with proxi- diphenyl oxide. Moreover, this approach suggested has
mal crown esters, whereas 2-acetamido-3,4,6-tri-O- marked advantages over the known synthesis of N-
acetyl-2-deoxy-D-glucopyranose was the major prod- acetylglucosamine trans-aryl glycosides under the
Table 1. The yields of glycosides (V)–(VII) and the reaction times (100% substrate conversion, TLC monitoring) of phenol
glycosylation with (I) under phase transfer conditions
(
V)
time, h
(VI)
time, h
(VII)
time, h
Catalyst
yield, %
yield, %
yield, %
B18C6
66
43
73
83
81
45
4
83
84
86
75
67
76
6
74
49
72
68
69
43
5
[
[
[
3.3] DB18C6
2.4] DB18C6
1.5] DB18C6
7
4
6
7
4
6
9
5
5
2.5
2.5
7
4.5
4.5
7
BP20C6
5C5
1
1
Table 2. The H NMR spectra of β-glycosides (V)–(VII) (CDCl , Me Si, working frequency 300 MHz)
3
4
Chemical shifts, ppm (J, Hz)
Proton
(
V)
(VI)
(VII)
H1 (J1, 2
H2 (J2, 3
H3 (J3, 4
H4 (J4, 5
)
5.28d (8)
5.47d (8)
5.15d (9)
)
4.14ddd (10)
5.42dd (9.5)
5.15dd (9.5)
4.12ddd (10)
4.09ddd (10)
5.40dd (10)
5.14dd (10)
)
)
5.46dd (9.5)
5.15dd (9.5)
H5 (J5, 6a; J5, 6b
)
3.88ddd (2.5; 5.0)
4.16dd, 4.29dd (12)
1.95s, 2.05s, 2.06s, 2.08s
5.75d (9)
3.95ddd (2.5; 5)
4.17dd, 4.29dd (12)
1.97s, 2.07s, 2.09s, 6 H
5.70d (8.5)
3.81ddd (2.5; 5.5)
H6a,b (J6a, 6b
)
4.15dd, 4.30dd (12)
NAc, OAC
1.97s, 2.04s, 2.06s, 2.08s, 12 H
5.79d (9)
NH (J2, NH
CHarom
R
)
7.01m, 7.28m
7.10d, 8.19d
6.81d, 6.23d, 4 H
3.77s, 3 H
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 30 No. 3 2004

AROMATIC CROWN ETHERS AS PHASE TRANSFER CATALYSTS
303
phase transfer conditions (in liquid–liquid system) at
REFERENCES
the catalysis with tertiary ammonium salts [6, 7].
1
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General Glycosylation Procedure
2
A mixture of 2-acetamido-3,4,6-tri-O-acetyl-2-
deoxy-α-D-glucopyranosyl chloride (500 mg,
1
.37 mmol) [5], anhydrous potassium carbonate
3
(
(
189 mg, 1.37 mmol), the corresponding phenol
1.37 mmol), and crown ether (0.274 mmol) in anhy-
drous acetonitrile (20 ml) was stirred at 25°ë up to the
complete conversion of substrate (TLC monitoring).
The solid residue was filtered off, the solvent was
removed under a reduced pressure, and glycosides (V)–
4
(
VII) were isolated by column chromatography on sil-
ica gel.
Phenyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-
b-D-glucopyranoside (V); mp 205–206°C; [[α]
5
. Horton, D., Methods in Carbohydrate Chemistry, vol. 6,
Whistler, R.L. and Bemiller, J.N., Eds., New York: Aca-
demic, 1972. Translated under the title Metody issledo-
vaniya uglevodov, Moscow: Mir, 1975, pp. 221–224.
546
−
13° (Ò 0.95, chloroform). Lit. [8]: yield 73%; mp 203–
2
04°ë; [α] –14.5° (c 0.95, chloroform).
D
6
7
8
. Roy, R. and Tropper, F., Synth. Commun., 1990, vol. 20,
p-Nitrophenyl 2-acetamido-3,4,6-tri-O-acetyl-2-
pp. 2097–2102.
deoxy-b-D-glucopyranoside (VI); mp 235–237°C,
. Roy, R. and Tropper, F.D., Can. J. Chem., 1991, vol. 69,
pp. 817–821.
[
α] –49° (c 1.0, chloroform). Lit. [9]: yield 39%; mp
546
2
2
40°C; [α] –46.2° (acetone); [10]: yield 76–78%; mp
D
. Zurabyan, S.E.,Antonenko, T.S., and Khorlin,A.Ya., Izv.
Akad. Nauk SSSR, Ser. Khim., 1969, no. 9, pp. 2043–
38–239°C.
2
044.
p-Methoxyphenyl
2-acetamido-3,4,6-tri-O-
acetyl-2-deoxy-b-D-glucopyranoside (VII); mp 193–
9. Leaback, D.H. and Walker, P.G., J. Chem. Soc., 1957,
no. 12, pp. 4754–4760.
1
8
94°ë, [α] –12° (c 1.0, chloroform). Lit. [6]: yield
5
46
1
0. Zurabyan, S.E., Volosyuk, T.P., and Khorlin, A.Ya., Izv.
Akad. Nauk SSSR, Ser. Khim., 1968, no. 7, pp. 1612–
1614.
5%; mp 195.8–196.4°C, [α] –11° (chloroform).
D
1
For the H NMR spectra, see Table 2.
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 30 No. 3 2004