Glycosylation

It has been revealed that the oligosaccharide is an important factor in many areas of life processes, embryonic growth, differentiation, aging, immunity and carcinogenesis. Many researches have been conducted to understand the functions in biological systems and structure-activity relationship of oligosaccharides. For the structure-based studies, it is necessary to synthesize oligosaccharides with confirmed structure so as to evaluate their activity. Throughout the synthesis of oligosaccharides, glycosylation, protection and deprotection processes are repeated for every glycosidic linkage formed. Thus, in order to synthesize oligosaccharides effectively, the glycosyl donor and acceptor, as well as the protecting agents are vitally important. For this reason, there is much research activity in finding glycosyl donors and acceptors with suitable properties.
In recent years, the glucose derivative 1, with thioformimidate as a leaving group, was developed by Mukaiyama and his co-workers.1) This reagent is a glycosyl donor with high reactivity and stability. 1 is activated with a catalytic amount of TfOH in the presence of MS5A and reacts with a glycosyl acceptor to provide a disaccharide in a quantitative yield. Furthermore, by choosing the appropriate solvents, α- or β-glycosides can be obtained selectively. The glycosyl acceptors with a fluorine atom or an ethylthio group at 1-position were also used and the resulting disaccharides can also be used as glycosyl donors.

In addition, the utility of p-methoxyphenyl glycosides has been reported.2) The p-methoxyphenyl group is a useful anomeric protective group which is stable under most of the conditions used in oligosaccharide synthesis. It is removed selectively by treatment with 2,3-dichloro-5,6-dicyano-pbenzoquinone and ceric ammonium nitrate (IV), to give the corresponding hemiacetals. Also the p-methoxyphenyl glycosides are converted in one step into the corresponding glycosyl halides and thiophenyl glycosides in high yields and can be used as glycosyl donors.

The followings are glycosyl donors in which the anomeric position is activated, including 1, p-methoxyphenyl glycosides, glycosyl acceptors and activating agents that can be obtained from TCI. TCI is pleased to supply these reagents for your needs in the research of oligosaccharides and related studies.

Glycosyl Donors

Reagents for Glycosyl Donor Synthesis

MP Glycosides & Related Reagents

Glycosyl Acceptors

Activating Agents

Enzyme

Enzyme Substrates

Glycosyl Donors

・Imidate Sugars

T2295 T2295 T2491 T2491 T1991 T1991
T1999 T1999 T2695 T2695 T2615 T2615
T2295 2,3,4,6-Tetra-O-acetyl-alpha-D-galactopyranosyl 2,2,2-Trichloroacetimidate
T2491 2,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyl 2,2,2-Trichloroacetimidate
T1991 2,3,4,6-Tetra-O-benzoyl-alpha-D-glucopyranosyl p-Trifluoromethylbenzylthio-N-(p-trifluoromethylphenyl)formimidate
T1999 2,3,4,6-Tetra-O-benzyl-alpha-D-glucopyranosyl p-Trifluoromethylbenzylthio-N-(p-trifluoromethylphenyl)formimidate
T2695 2,3,4-Tri-O-acetyl-beta-L-arabinopyranosyl 2,2,2-Trichloroacetimidate
T2615 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranosyl 2,2,2-Trichloroacetimidate
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・Thioglycosides

I0328 I0328 M1706 M1706 M1759 M1759
M1682 M1682 M1501 M1501 M1649 M1649
M1626 M1626 M1628 M1628 P1660 P1660
P1475 P1475 P1643 P1643 P1762 P1762
P1477 P1477 P1476 P1476 P1679 P1679
P1680 P1680 P1736 P1736 P1642 P1642
P1866 P1866 P1842 P1842
I0328 Isopropyl 1-Thio-beta-D-galactopyranoside
M1706 Methyl 5-Acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-S-phenyl-2-thio-D-glycero-D-galacto-2-nonulopyranosylonate
M1759 Methyl (Phenyl 2,3,4-Tri-O-acetyl-1-thio-beta-D-glucopyranosid)uronate
M1682 Methyl 2,3,4,6-Tetra-O-acetyl-1-thio-beta-D-glucopyranoside
M1501 Methyl 2,3,4,6-Tetra-O-acetyl-1-thio-alpha-D-mannopyranoside (contains ca. 5% beta-isomer)
M1649 Methyl 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside
M1626 Methyl 2,3,4-Tri-O-acetyl-1-thio-beta-L-fucopyranoside
M1628 Methyl 2,3,4-Tri-O-benzyl-1-thio-beta-L-fucopyranoside
P1660 Phenyl 3-O-Allyl-2,4,6-tri-O-benzyl-1-thio-beta-D-galactopyranoside
P1475 Phenyl 4,6-O-Benzylidene-1-thio-beta-D-glucopyranoside
P1643 Phenyl 2-Deoxy-1-thio-2-(2,2,2-trichloroethoxyformamido)-beta-D-galactopyranoside
P1762 Phenyl N-Benzyl-2-amino-4,6-O-benzylidene-2-N,3-O-carbonyl-2-deoxy-1-thio-beta-D-glucopyranoside
P1477 Phenyl 2,3,4,6-Tetra-O-acetyl-1-thio-beta-D-galactopyranoside
P1476 Phenyl 2,3,4,6-Tetra-O-acetyl-1-thio-beta-D-glucopyranoside
P1679 Phenyl 2,3,4,6-Tetra-O-benzyl-1-thio-beta-D-galactopyranoside
P1680 Phenyl 2,4,6-Tri-O-acetyl-3-O-allyl-1-thio-beta-D-galactopyranoside
P1736 Phenyl 2,4,6-Tri-O-acetyl-3-O-allyl-1-thio-beta-D-glucopyranoside
P1642 Phenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxyformamido)-beta-D-galactopyranoside
P1866 Phenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxyformamido)-beta-D-glucopyranoside
P1842 Phenyl 2,3,4-Tri-O-benzyl-1-thio-beta-L-fucopyranoside
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・Halogeno Sugars

A1416 A1416 T1961 T1961 T1995 T1995
T2567 T2567 T1922 T1922 T1923 T1923
T1971 T1971 T2568 T2568
A1416 2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha-D-glucopyranosyl Chloride
T1961 2,3,4,6-Tetra-O-acetyl-alpha-D-glucopyranosyl Bromide (stabilized with CaCO3)
T1995 2,3,4,6-Tetra-O-acetyl-alpha-D-glucopyranosyl Fluoride
T2567 2,3,4,6-Tetra-O-acetyl-D-mannopyranosyl Fluoride
T1922 2,3,4,6-Tetra-O-benzyl-alpha-D-glucopyranosyl Fluoride
T1923 2,3,4,6-Tetra-O-benzyl-beta-D-glucopyranosyl Fluoride
T1971 2,3,4,6-Tetra-O-benzyl-D-glucopyranosyl Fluoride
T2568 2,3,4,6-Tetra-O-pivaloyl-D-mannopyranosyl Fluoride
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・Others

R0067 R0067 R0080 R0080 R0066 R0066
T2197 T2197
R0067 beta-D-Ribofuranose 1-Acetate 2,3,5-Tribenzoate
R0080 beta-L-Ribofuranose 1-Acetate 2,3,5-Tribenzoate
R0066 Tetra-O-acetyl-beta-D-ribofuranose
T2197 2,3,4,6-Tetra-O-benzyl-alpha-D-glucopyranosyl N,N,N',N'-Tetramethylphosphorodiamidate (ca. 20% in Benzene)
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Reagents for Glycosyl Donor Synthesis

B2440 B2440 B3664 B3664 D1868 D1868
D2159 D2159 H0182 H0182 M1573 M1573
P1243 P1243 T1308 T1308 T0372 T0372
T2638 T2638 T2547 T2547
B2440 Bis(2-methoxyethyl)aminosulfur Trifluoride
B3664 4-tert-Butyl-2,6-dimethylphenylsulfur Trifluoride
D1868 (Diethylamino)sulfur Trifluoride [Fluorinating Reagent]
D2159 Dimethylthiophosphinoyl Chloride
H0182 Hydrogen Bromide (30% in Acetic Acid, ca. 5.1mol/L) [for Peptide research]
M1573 Morpholinosulfur Trifluoride
P1243 4-Penten-1-ol
T1308 Tetramethyldiphosphine Disulfide
T0372 Trichloroacetonitrile
T2638 2,2,2-Trifluoro-N-(4-methoxyphenyl)acetimidoyl Chloride
T2547 2,2,2-Trifluoro-N-phenylacetimidoyl Chloride
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MP Glycosides & Related Reagents

・Galactose

M1620 M1620 M1590 M1590 M1633 M1633
M1596 M1596 M1477 M1477 M1588 M1588
M1620 4-Methoxyphenyl 3-O-Allyl-2-O-benzyl-4,6-O-benzylidene-beta-D-galactopyranoside
M1590 4-Methoxyphenyl 3-O-Allyl-4,6-O-benzylidene-2-O-(4-methylbenzoyl)-beta-D-galactopyranoside
M1633 4-Methoxyphenyl 2,6-Di-O-benzyl-3,4-O-isopropylidene-beta-D-galactopyranoside
M1596 4-Methoxyphenyl 3,4-O-Isopropylidene-2,6-bis-O-(4-methylbenzoyl)-beta-D-galactopyranoside
M1477 4-Methoxyphenyl 2,3,4,6-Tetra-O-acetyl-beta-D-galactopyranoside
M1588 4-Methoxyphenyl 2,3,4,6-Tetra-O-benzyl-beta-D-galactopyranoside
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・Galactosamine

M1643 M1643
M1643 4-Methoxyphenyl 3-O-Allyl-2-azido-4,6-O-benzylidene-2-deoxy-beta-D-galactopyranoside
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・Glucose

M1630 M1630 M1642 M1642
M1630 4-Methoxyphenyl 2,3,4,6-Tetra-O-acetyl-beta-D-glucopyanoside
M1642 4-Methoxyphenyl 2,4,6-Tri-O-acetyl-3-O-benzyl-beta-D-glucopyranoside
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・Glucosamine

M1834 M1834 M1638 M1638 M1598 M1598
M1609 M1609 M1480 M1480
M1834 4-Methoxyphenyl 4-O-Acetyl-3,6-di-O-benzyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside
M1638 4-Methoxyphenyl 3-O-Allyl-2-azido-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranoside
M1598 4-Methoxyphenyl 3-O-Allyl-4,6-O-benzylidene-2-deoxy-2-phthalimido-beta-D-glucopyranoside
M1609 4-Methoxyphenyl 3-O-Benzyl-4,6-O-benzylidene-2-deoxy-2-phthalimido-beta-D-glucopyranoside
M1480 4-Methoxyphenyl 3,4,6-Tri-O-acetyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside
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・Mannose

M1647 M1647
M1647 4-Methoxyphenyl 2,3,4,6-Tetra-O-acetyl-alpha-D-mannopyranoside
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・Disaccharides

G0330 G0330 M1694 M1694 G0309 G0309
G0311 G0311 G0379 G0379 G0299 G0299
M1761 M1761 M1763 M1763 N0816 N0816
N0846 N0846
G0330 Gal[2346Ac]beta(1-3)GalN3[46Bzd]-beta-MP
M1694 Gal[2346Ac]beta(1-4)Glc[236Ac]-beta-MP
G0309 Gal[2346Ac]beta(1-3)GlcN3[46Bzd]-beta-MP
G0311 Gal[2346Ac]beta(1-3)GlcNPhth[46Bzd]-beta-MP
G0379 Gal[3All,246Bn]beta(1-3)GlcNPhth[6Bn]-beta-MP
G0299 GlcNPhth[346Ac]beta(1-3)Gal[246Bn]-beta-MP
M1761 Neu5Ac[1Me,4789Ac]alpha(2-6)Gal[24Bz,3Bn]-beta-MP
M1763 Neu5GcAc[1Me,4789Ac]alpha(2-6)Gal[24Bz,3Bn]-beta-MP
N0816 Neu5GcAc[1Me,4789Ac]alpha(2-3)Gal[246Bz]-beta-MP
N0846 Neu5Ac[1Me,4789Ac]alpha(2-3)Gal[246Bz]-beta-MP
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・Deprotecting Reagents

C1806 C1806 D1070 D1070
C1806 Ammonium Cerium(IV) Nitrate
D1070 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone
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Glycosyl Acceptors

・Galactose

M1589 M1589 M1482 M1482 M1725 M1725
M1710 M1710 M1597 M1597 M1634 M1634
M1593 M1593 M1594 M1594 M1592 M1592
M2104 M2104 M1933 M1933
M1589 4-Methoxyphenyl 3-O-Allyl-4,6-O-benzylidene-beta-D-galactopyranoside
M1482 4-Methoxyphenyl 3-O-Allyl-beta-D-galactopyranoside
M1725 4-Methoxyphenyl 3-O-Benzyl-beta-D-galactopyranoside
M1710 4-Methoxyphenyl 4,6-O-Benzylidene-beta-D-galactopyranoside
M1597 4-Methoxyphenyl 2,6-Bis-O-(4-methylbenzoyl)-beta-D-galactopyranoside
M1634 4-Methoxyphenyl 2,6-Di-O-benzyl-beta-D-galactopyranoside
M1593 4-Methoxyphenyl 3,4-O-Isopropylidene-beta-D-galactopyranoside
M1594 4-Methoxyphenyl 3,4-O-Isopropylidene-6-O-(4-methylbenzoyl)-beta-D-galactopyranoside
M1592 4-Methoxyphenyl 2,4,6-Tri-O-benzyl-beta-D-galactopyranoside
M2104 4-Methoxyphenyl 2,3,6-Tri-O-benzyl-beta-D-galactopyranoside
M1933 Methyl 2,3,6-Tri-O-benzoyl-alpha-D-galactopyranoside
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・Galactosamine

A1833 A1833 A1832 A1832 P1643 P1643
A1833 O-(2-Azido-4,6-O-benzylidene-2-deoxy-alpha-D-galactopyranosyl)-N-[(9H-fluoren-9-ylmethoxy)carbonyl]-L-serine tert-Butyl Ester
A1832 O-(2-Azido-4,6-O-benzylidene-2-deoxy-alpha-D-galactopyranosyl)-N-[(9H-fluoren-9-ylmethoxy)carbonyl]-L-threonine tert-Butyl Ester
P1643 Phenyl 2-Deoxy-1-thio-2-(2,2,2-trichloroethoxyformamido)-beta-D-galactopyranoside
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・Glucose

D1949 D1949 I0400 I0400 M1640 M1640
M1641 M1641 M1125 M1125 M1487 M1487
M1488 M1488 P1475 P1475
D1949 1,2:5,6-Di-O-isopropylidene-alpha-D-glucofuranose
I0400 1,2-O-Isopropylidene-alpha-D-glucofuranose
M1640 4-Methoxyphenyl 3-O-Benzyl-4,6-O-benzylidene-beta-D-glucopyranoside
M1641 4-Methoxyphenyl 3-O-Benzyl-beta-D-glucopyranoside
M1125 Methyl 4,6-O-Benzylidene-alpha-D-glucopyranoside
M1487 Methyl 2,3,4-Tri-O-benzoyl-alpha-D-glucopyranoside
M1488 Methyl 2,3,4-Tri-O-benzyl-alpha-D-glucopyranoside
P1475 Phenyl 4,6-O-Benzylidene-1-thio-beta-D-glucopyranoside
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・Glucosamine

A1811 A1811 M1616 M1616 M1637 M1637
M1617 M1617 M1610 M1610 M1479 M1479
M1615 M1615 P0130 P0130
A1811 2-Acetamido-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranosyl Azide
M1616 4-Methoxyphenyl 2-Amino-3,6-di-O-benzyl-2-deoxy-beta-D-glucopyranoside
M1637 4-Methoxyphenyl 2-Azido-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranoside
M1617 4-Methoxyphenyl 2-Azido-3,6-di-O-benzyl-2-deoxy-beta-D-glucopyranoside
M1610 4-Methoxyphenyl 3-O-Benzyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside
M1479 4-Methoxyphenyl 4,6-O-Benzylidene-2-deoxy-2-phthalimido-beta-D-glucopyranoside
M1615 4-Methoxyphenyl 3,6-Di-O-benzyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside
P0130 Phenyl N-Acetyl-alpha-D-glucosaminide
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・Mannose

T1459 T1459
T1459 1,3,4,6-Tetra-O-acetyl-beta-D-mannopyranose
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・Disaccharides

M1686 M1686 M1726 M1726 M1727 M1727
M1686 Gal[26Bn]beta(1-4)Glc[236Bn]-beta-MP
M1726 Gal[236Bn]beta(1-4)Glc[236Bn]-beta-MP
M1727 Gal[246Bn]beta(1-4)Glc[236Bn]-beta-MP
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Activating Agents

B0527 B0527 B0656 B0656 C0903 C0903
T1292 T1292 H0914 H0914 I0074 I0074
T2029 T2029 T1331 T1331 T0751 T0751
T0871 T0871 T1173 T1173 Z0007 Z0007
B0527 Boron Trifluoride - Ethyl Ether Complex
B0656 N-Bromosuccinimide
C0903 2-Chloro-1-methylpyridinium Iodide
T1292 Copper(II) Trifluoromethanesulfonate
H0914 Hafnocene Dichloride
I0074 N-Iodosuccinimide
T2029 Methyl Trifluoromethanesulfonate
T1331 Silver Trifluoromethanesulfonate
T0751 Trifluoromethanesulfonic Acid
T0871 Trimethylsilyl Trifluoromethanesulfonate [Trimethylsilylating Agent]
T1173 Triphenylmethylium Tetrafluoroborate
Z0007 Zirconocene Dichloride
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Enzyme

A1844 endo-alpha-N-Acetylgalactosaminidase (=Endo-alpha) Recombinant: from Bifidobacterium longum expressed in Escherichia coli
A1651 endo-beta-N-Acetylglucosaminidase (=Endo-M) Recombinant: from Mucor hiemalis expressed in Candida boidinii [Purity: single band by SDS-PAGE(85KDa)]
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Enzyme Substrates

A1614 A1614 D3690 D3690 G0297 G0297
S0523 S0523
A1614 Nomega-(2-Acetamido-2-deoxy-beta-D-glucopyranosyl)-Nalpha-(tert-butoxycarbonyl)-L-asparagine
D3690 DNS-SGN
G0297 N-GlcNAc-Biotin
S0523 Sialylglycopeptide
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Literature

1) T. Mukaiyama, H. Chiba, S. Funasaka, Chem. Lett., 2002, 392 [DOI]; H. Chiba, S. Funasaka, K. Kiyota, T. Mukaiyama, Chem. Lett., 2002, 746 [DOI]; H. Chiba, T. Mukaiyama, Chem. Lett., 2003, 32, 172 [DOI]; H. Chiba, S. Funasaka, T. Mukaiyama, Bull. Chem. Soc. Jpn., 2003, 76, 1629 [DOI].
2) M. Mori, Y. Ito, T. Ogawa, Carbohydr. Res., 1989, 192, 131 [DOI]; Y. Matsuzaki, Y. Ito, T. Ogawa, Tetrahedron Lett., 1992, 33, 4025 [DOI]; A. Dan, Y. Ito, T. Ogawa, J. Org. Chem., 1995, 60, 4680 [DOI]; C. Murakata, T. Ogawa, Carbohydr. Res., 1992, 235, 95 [DOI]; H. Kuyama, T. Nukada, Y. Nakahara, T. Ogawa, Tetrahedron Lett., 1993, 34, 2171 [DOI]; Z. Zhang, G. Magnusson, Carbohydr. Res., 1996, 295, 41 [DOI]; H. Ando, Y. Koike, H. Ishida, M. Kiso, Tetrahedron Lett., 2003, 44, 6883 [DOI].

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