JPH0733792A - New glycosyl donor and method of glycosylation - Google Patents
New glycosyl donor and method of glycosylationInfo
- Publication number
- JPH0733792A JPH0733792A JP5203733A JP20373393A JPH0733792A JP H0733792 A JPH0733792 A JP H0733792A JP 5203733 A JP5203733 A JP 5203733A JP 20373393 A JP20373393 A JP 20373393A JP H0733792 A JPH0733792 A JP H0733792A
- Authority
- JP
- Japan
- Prior art keywords
- tetra
- glycopyranoside
- benzyl
- lewis acid
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 8
- 239000000348 glycosyl donor Substances 0.000 title abstract description 8
- 238000006206 glycosylation reaction Methods 0.000 title description 5
- 230000013595 glycosylation Effects 0.000 title 1
- -1 p-methoxybenzyl Chemical group 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002841 Lewis acid Substances 0.000 claims abstract description 11
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 11
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 2
- 239000004332 silver Substances 0.000 claims 2
- 229910052709 silver Inorganic materials 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 125000006512 3,4-dichlorobenzyl group Chemical group [H]C1=C(Cl)C(Cl)=C([H])C(=C1[H])C([H])([H])* 0.000 claims 1
- 125000002774 3,4-dimethoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1OC([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000003852 3-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])* 0.000 claims 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 claims 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- CSHCNFMXWURBBD-CAIHAHRASA-N (3r,4s,5r,6r)-2-cyclohexyloxy-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane Chemical compound C([C@@H]1[C@H]([C@H](OCC=2C=CC=CC=2)[C@@H](OCC=2C=CC=CC=2)C(OC2CCCCC2)O1)OCC=1C=CC=CC=1)OCC1=CC=CC=C1 CSHCNFMXWURBBD-CAIHAHRASA-N 0.000 abstract 1
- 239000004210 ether based solvent Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
- 150000002338 glycosides Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- OGOMAWHSXRDAKZ-RUOAZZEASA-N (2s,3r,4s,5r,6r)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol Chemical compound C([C@H]1O[C@@H]([C@@H]([C@@H](OCC=2C=CC=CC=2)[C@@H]1OCC=1C=CC=CC=1)OCC=1C=CC=CC=1)O)OCC1=CC=CC=C1 OGOMAWHSXRDAKZ-RUOAZZEASA-N 0.000 description 2
- HMEOEMKYYQXUAN-HENWMNBSSA-N (3r,4s,5s,6r)-2-benzyl-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)OC1(O)CC1=CC=CC=C1 HMEOEMKYYQXUAN-HENWMNBSSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000386 donor Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CLLLODNOQBVIMS-UHFFFAOYSA-N 2-(2-methoxyethoxy)acetic acid Chemical compound COCCOCC(O)=O CLLLODNOQBVIMS-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- PGRDNHQIURCHPZ-UHFFFAOYSA-N cyclohexyloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1CCCCC1 PGRDNHQIURCHPZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000008135 α-glycosides Chemical class 0.000 description 1
- 150000008505 β-D-glucopyranosides Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Saccharide Compounds (AREA)
- Steroid Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルファ−Ｄ−グリコ
ピラノシド誘導体もしくはベータ−Ｄ−グリコピラノシ
ド誘導体の簡便で高収率、かつ、高選択的な合成方法、
およびグリコシド供与体として好適な新規な化合物に関
するものである。Ｄ−グリコピラノシド構造は、抗生物
質、糖タンパク質、オリゴ糖、多糖類等多くの生理活性
物質に含まれる。Ｄ−グリコピラノシド誘導体は医薬
品、化粧品、食品添加物等多くの分野で用いられてい
る。FIELD OF THE INVENTION The present invention relates to a method for synthesizing an alpha-D-glycopyranoside derivative or a beta-D-glycopyranoside derivative in a simple and high yield and with high selectivity.
And novel compounds suitable as glycoside donors. The D-glycopyranoside structure is contained in many physiologically active substances such as antibiotics, glycoproteins, oligosaccharides and polysaccharides. D-glycopyranoside derivatives are used in many fields such as pharmaceuticals, cosmetics and food additives.
【０００２】[0002]
【従来の技術】従来、Ｄ−グリコピラノシド誘導体の合
成方法としては、下記に示す方法が知られている。 Ｓ．Ｈａｓｈｉｍｏｔｏ，Ｍ．Ｈａｙａｓｈｉ，ａｎｄ
Ｒ．Ｎｏｙｏｒｉ，ＴｅｔｒａｈｅｄｒｏｎＬｅｔ
ｔ．，２５，１３７９（１９８４）． Ｔ．Ｍａｔｓｕｍｏｔｏ，Ｈ．Ｍａｅｔａ，ａｎｄ
Ｋ．Ｓｕｚｕｋｉ，ＴｅｔｒａｈｅｄｒｏｎＬｅｔ
ｔ．，２９，３５６７；３５７１；３５７５（１９８
８）． Ｋ．Ｓｕｚｕｋｉ，Ｈ．Ｍａｅｔａ，ａｎｄ Ｔ．Ｍａ
ｔｕｓｕｍｏｔｏ，ＴｅｔｒａｈｅｄｒｏｎＬｅｔ
ｔ．，３０，４８５３（１９８９）． Ｓ．Ｋｏｂａｙａｓｈｉ，Ｋ．Ｋｏｉｄｅ，ａｎｄ
Ｍ．Ｏｈｎｏ，ＴｅｔｒａｈｅｄｒｏｎＬｅｔｔ．，３
１，２４３５（１９９０）；Ｋ．Ｋｏｉｄｅ，Ｍ．Ｏｈ
ｎｏ，ａｎｄ Ｓ．Ｋｏｂａｙａｓｈｉ，Ｔｅｔｒａｈ
ｅｄｏｎＬｅｔｔ．，３２，７０７５（１９９１）． Ｋ．Ｆｕｋａｓｅ，Ａ．Ｈａｓｕｏｋａ，Ｉ．Ｋｉｎｏ
ｓｈｉｔａ，ａｎｄＳ．Ｋｕｓｕｍｏｔｏ，Ｔｅｔｒａ
ｈｅｄｏｎＬｅｔｔ．，３３，７１６５（１９９２）．2. Description of the Related Art Conventionally, the following method has been known as a method for synthesizing a D-glycopyranoside derivative. S. Hashimoto, M .; Hayashi, and
R. Noyori, Tetrahedron Let
t. , 25 , 1379 (1984). T. Matsumoto, H .; Maeta, and
K. Suzuki, Tetrahedron Let
t. , 29 , 3567; 3571; 3575 (198).
8). K. Suzuki, H .; Maeta, and T.M. Ma
tusumoto, TetrahedronLet
t. , 30 , 4853 (1989). S. Kobayashi, K .; Koide, and
M. Ohno, Tetrahedron Lett. , 3
1 , 2435 (1990); Koide, M .; Oh
no, and S.N. Kobayashi, Tetrah
edonLett. , 32 , 7075 (1991). K. Fukase, A .; Hasuoka, I .; Kino
shita, and S. Kusumoto, Tetra
hedon Lett. , 33 , 7165 (1992).
【０００３】[0003]
【発明が解決しようとする課題】従来の技術でＤ−グリ
コピラノシド誘導体を合成する場合、グリコシル供与体
が不安定であったり、目的物の合成収率が低かったり、
また、用いる触媒が等モル量以上必要で反応触媒のコス
トが高いなどの欠点があった。本発明の目的は、アルフ
ァ−Ｄ−グリコピラノシド誘導体もしくはベータ−Ｄ−
グリコピラノシド誘導体を収率よく、簡便に合成する方
法を提供することにある。When synthesizing a D-glycopyranoside derivative by a conventional technique, the glycosyl donor is unstable, the synthesis yield of the target compound is low,
Further, there is a defect that the catalyst used is required in an equimolar amount or more and the cost of the reaction catalyst is high. The object of the present invention is to provide an alpha-D-glycopyranoside derivative or beta-D-
An object of the present invention is to provide a method for synthesizing a glycopyranoside derivative in high yield and easily.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、Ｄ−グリ
コピラノシド誘導体を合成する方法を開発するため、１
−Ｏ−アシル−２，３，４，６−テトラ−Ｏ−ベンジル
−Ｄ−グリコピラノシドと各種アルコールのトリメチル
シリルエーテルの反応を触媒量の種々の酸性触媒の存在
下で試み、本発明を完成した。反応に用いる触媒として
は、四塩化錫、四塩化チタン、四塩化硅素、３弗化ホウ
ソなどのルイス酸あるいはルイス酸と過塩素酸銀または
トリフルオロメタンスルホン酸銀の混合触媒が好まし
く、後者の混合触媒が特に好ましい。触媒の量は、グリ
コシル供与体に対し、総計して１〜６０モル％が望まし
く、さらに望ましくは１０〜６０モル％である。四塩化
錫、四塩化チタン、四塩化硅素、３弗化ホウソなどのル
イス酸と、過塩素酸銀またはトリフルオロメタンスルホ
ン酸銀の調合比は、モル比で１：１から１：２が望まし
い。In order to develop a method for synthesizing a D-glycopyranoside derivative, the present inventors have
The present invention was completed by trying the reaction of -O-acyl-2,3,4,6-tetra-O-benzyl-D-glycopyranoside with trimethylsilyl ethers of various alcohols in the presence of catalytic amounts of various acidic catalysts. The catalyst used in the reaction is preferably a Lewis acid such as tin tetrachloride, titanium tetrachloride, silicon tetrachloride, borosodium trifluoride, or a mixed catalyst of Lewis acid and silver perchlorate or silver trifluoromethanesulfonate, and the latter mixture is preferable. Catalysts are particularly preferred. The total amount of the catalyst is preferably 1 to 60 mol% and more preferably 10 to 60 mol% based on the glycosyl donor. The mixing ratio of Lewis acid such as tin tetrachloride, titanium tetrachloride, silicon tetrachloride, borosodium trifluoride and the like and silver perchlorate or silver trifluoromethanesulfonate is preferably 1: 1 to 1: 2.
【０００５】グリコシル供与体としては、１−Ｏ−アシ
ル−２，３，４，６−テトラ−Ｏ−アルキル−Ｄ−ガラ
クトピラノシド、１−Ｏ−アシル−２，３，４，６−テ
トラ−Ｏ−アルキル−Ｄ−マンノピラノシド、１−Ｏ−
アシル−２，３，４，６−テトラ−Ｏ−アルキル−Ｄ−
グルコピラノシドなどを用いることができる。アシル基
としては、アセチル基、ブロモアセチル基、ヨードアセ
チル基、メトキシアセチル基、３−メトキシプロピオニ
ル基、メチルチオアセチル基、（２−メトキシエトキ
シ）アセチル基、２−メトキシベンゾイル基などを用い
ることができる。さらに好ましくは、アシル基としては
（２−メトキシエトキシ）アセチル基である。アルキル
基としては、ベンジル、メチル基、メトキシベンジル基
などが望ましい。Glycosyl donors include 1-O-acyl-2,3,4,6-tetra-O-alkyl-D-galactopyranoside and 1-O-acyl-2,3,4,6-. Tetra-O-alkyl-D-mannopyranoside, 1-O-
Acyl-2,3,4,6-tetra-O-alkyl-D-
Glucopyranoside or the like can be used. As the acyl group, an acetyl group, a bromoacetyl group, an iodoacetyl group, a methoxyacetyl group, a 3-methoxypropionyl group, a methylthioacetyl group, a (2-methoxyethoxy) acetyl group, a 2-methoxybenzoyl group, or the like can be used. . More preferably, the acyl group is a (2-methoxyethoxy) acetyl group. As the alkyl group, benzyl, methyl group, methoxybenzyl group and the like are desirable.
【０００６】グリコシド受容体としては、種々のアルコ
ールのトリメチルシリルエーテルを用いることができ
る。グリコシド受容体は、供与体に対し等モル量でよい
が、過剰量用いてもよい。反応に用いる溶媒としては、
アルファーグリコシドを得る場合は、ジメトキシエタ
ン、ジグリム、ジオキサン、エーテル、テトラヒドロフ
ラン等のエーテル系溶媒が好ましく、エーテルが最も好
適である。ベータグリコシドを得る場合は、トルエン、
ベンゼン等の芳香族系溶媒や、塩化メチレン、ジクロル
エタン等の塩素系溶媒もしくはニトロメタン、アセトニ
トリルが好ましい。反応の温度は、−２５℃から０℃が
望ましい。また、反応時間は、１〜５０時間が望まし
く、さらに望ましくは１０〜１５時間である。As the glycoside acceptor, trimethylsilyl ethers of various alcohols can be used. The glycoside acceptor may be equimolar to the donor, but may be used in excess. As the solvent used in the reaction,
When obtaining an alpha glycoside, an ether solvent such as dimethoxyethane, diglyme, dioxane, ether or tetrahydrofuran is preferable, and ether is most preferable. To obtain beta-glycoside, toluene,
Aromatic solvents such as benzene, chlorine based solvents such as methylene chloride and dichloroethane, or nitromethane and acetonitrile are preferable. The reaction temperature is preferably -25 ° C to 0 ° C. The reaction time is preferably 1 to 50 hours, more preferably 10 to 15 hours.
【０００７】[0007]
【実施例】次に、実施例によって本発明をさらに詳細に
説明する。 （実施例１） １−Ｏ−（２−（２−メトキシエトキシ）アセチル）−
２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ−グルコピ
ラノースを用いる１−Ｏ−シクロヘキシル−２，３，
４，６−テトラ−Ｏ−ベンジル−Ｄ−グルコピラノース
の合成 四塩化錫（５２．１ｍｇ、０．２ｍｍｏｌ）のメチレン
クロリド溶液（３ｍｌ）に過塩素酸銀（８２．９ｍｇ、
０．４ｍｍｏｌ）を加え、室温で１時間攪拌した。得ら
れた溶液を−２３℃まで冷却した後、１−Ｏ−（２−
（２−メトキシエトキシ）アセチル）−２，３，４，６
−テトラ−Ｏ−ベンジル−Ｄ−グルコピラノース（アル
ファ体とベータ体の混合物、６５７ｍｇ、１ｍｍｏｌ）
とＯ−トリメチルシリルシクロヘキサノール（１７２ｍ
ｇ、１ｍｍｏｌ）の塩化メチレン溶液を加えた。溶液を
−２３℃で１０時間攪拌した。得られた溶液を飽和重曹
水に加え反応を止めた。塩化メチレンにて抽出し、有機
層を３回水洗した。無水硫酸ナトリウムにて溶液を乾燥
し、溶媒を減圧下留去した。残渣をシリカゲルカラムク
ロマトグラフィーにて精製し、１−Ｏ−シクロヘキシル
−２，３，４，６−テトラ−Ｏ−ベンジル−ベータ−Ｄ
−グルコピラノースと１−Ｏ−シクロヘキシル−２，
３，４，６−テトラ−Ｏ−ベンジル−アルファ−Ｄ−グ
ルコピラノースの混合物を得た。（５２９ｍｇ、８５
％）生成物のＮＭＲスペクトルを測定し、アノマー水素
の積分比より両異性体の存在比を求めたところ、アルフ
ァ：ベータは２４：７６であった。 ＮＭＲスペクトル （重クロロフォルム）２７０ＭＨｚ アルファ体 δ（ｐｐｍ） ６．４６（ｄ，Ｊ＝３．３
Ｈｚ，Ｈ−１） べータ体 δ（ｐｐｍ） ５．６８（ｄ，Ｊ＝７．９
Ｈｚ，Ｈ−１）EXAMPLES Next, the present invention will be described in more detail by way of examples. (Example 1) 1-O- (2- (2-methoxyethoxy) acetyl)-
1-O-cyclohexyl-2,3 with 2,3,4,6-tetra-O-benzyl-D-glucopyranose
Synthesis of 4,6-tetra-O-benzyl-D-glucopyranose In a solution of tin tetrachloride (52.1 mg, 0.2 mmol) in methylene chloride (3 ml), silver perchlorate (82.9 mg,
0.4 mmol) was added and the mixture was stirred at room temperature for 1 hour. The resulting solution was cooled to -23 ° C and then 1-O- (2-
(2-Methoxyethoxy) acetyl) -2,3,4,6
-Tetra-O-benzyl-D-glucopyranose (mixture of alpha form and beta form, 657 mg, 1 mmol)
And O-trimethylsilylcyclohexanol (172m
g, 1 mmol) in methylene chloride was added. The solution was stirred at -23 ° C for 10 hours. The resulting solution was added to saturated aqueous sodium hydrogen carbonate to stop the reaction. It was extracted with methylene chloride, and the organic layer was washed with water three times. The solution was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography and 1-O-cyclohexyl-2,3,4,6-tetra-O-benzyl-beta-D.
-Glucopyranose and 1-O-cyclohexyl-2,
A mixture of 3,4,6-tetra-O-benzyl-alpha-D-glucopyranose was obtained. (529 mg, 85
%) The NMR spectrum of the product was measured, and the abundance ratio of both isomers was determined from the integral ratio of the anomeric hydrogen. As a result, alpha: beta was 24:76. NMR spectrum (heavy chloroform) 270 MHz alpha form δ (ppm) 6.46 (d, J = 3.3)
Hz, H-1) beta body δ (ppm) 5.68 (d, J = 7.9)
Hz, H-1)
【０００８】（実施例２） 各種１−Ｏ−アシル−２，３，４，６−テトラ−Ｏ−ベ
ンジル−Ｄ−グルコピラノースを用いる１−Ｏ−シクロ
ヘキシル−２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ
−グルコピラノースの合成 実施例１と同様に各種１−Ｏ−アシル−２，３，４，６
−テトラ−Ｏ−ベンジル−Ｄ−グルコピラノースをグリ
コシル供与体としてグリコシル化反応を行ない（化３
式）、表１に示す結果を得た。(Example 2) 1-O-cyclohexyl-2,3,4,6-tetra using various 1-O-acyl-2,3,4,6-tetra-O-benzyl-D-glucopyranose -O-benzyl-D
-Synthesis of glucopyranose Various 1-O-acyl-2,3,4,6 as in Example 1
-Tetra-O-benzyl-D-glucopyranose is used as a glycosyl donor to perform a glycosylation reaction (Chemical Formula 3
Formula), the results shown in Table 1 were obtained.
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】[0010]
【表１】 （実施例３） 各種ルイス酸を触媒とし、各種溶媒中での１−Ｏ−シク
ロヘキシル−２，３，４，６−テトラ−Ｏ−ベンジル−
Ｄ−グルコピラノースの合成 実施例１と同様に各種ルイス酸を触媒として各種溶媒中
で反応を行ない（化４式）、表２に示す結果を得た。[Table 1] (Example 3) 1-O-cyclohexyl-2,3,4,6-tetra-O-benzyl-in various solvents using various Lewis acids as catalysts
Synthesis of D-glucopyranose As in Example 1, various Lewis acids were used as catalysts in various solvents for reaction (Formula 4), and the results shown in Table 2 were obtained.
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】[0012]
【表２】 （実施例４） グリコシル供与体として１−Ｏ−（２−（２−メトキシ
エトキシ）アセチル）−２，３，４，６−テトラ−Ｏ−
ベンジル−Ｄ−グルコピラノース、溶媒としてアセトニ
トリルをを用いる各種アルコールのシリルエーテルのベ
ータグリコシル化反応 実施例３と同様に四塩化硅素と過塩素酸銀を触媒とし
て，アセトニトリル中で各種アルコールのシリルエーテ
ルと１−Ｏ−（２−（２−メトキシエトキシ）アセチ
ル）−２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ−グ
ルコピラノースの反応を行ない（化５式）、表３に示す
結果を得た。[Table 2] (Example 4) 1-O- (2- (2-methoxyethoxy) acetyl) -2,3,4,6-tetra-O- as a glycosyl donor
Beta-glycosylation reaction of silyl ethers of various alcohols using benzyl-D-glucopyranose and acetonitrile as a solvent In the same manner as in Example 3, using tetrachlorosilane and silver perchlorate as catalysts, silyl ethers of various alcohols in acetonitrile were used. 1-O- (2- (2-methoxyethoxy) acetyl) -2,3,4,6-tetra-O-benzyl-D-glucopyranose was reacted (Formula 5), and the results shown in Table 3 were obtained. Obtained.
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】[0014]
【表３】 （実施例５） グリコシル供与体として１−Ｏ−（２−（２−メトキシ
エトキシ）アセチル）−２，３，４，６−テトラ−Ｏ−
ベンジル−Ｄ−グルコピラノース、溶媒としてエーテル
を用いる各種アルコールのシリルエーテルのベータグリ
コシル化反応 実施例３と同様に四塩化硅素と過塩素酸銀を触媒とし
て、エーテル中で各種アルコールのシリルエーテルと１
−Ｏ−（２−（２−メトキシエトキシ）アセチル）−
２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ−グルコピ
ラノースの反応を行ない（化６式）、表４に示す結果を
得た。[Table 3] (Example 5) 1-O- (2- (2-methoxyethoxy) acetyl) -2,3,4,6-tetra-O- as a glycosyl donor.
Beta-glycosylation reaction of silyl ethers of various alcohols using benzyl-D-glucopyranose and ether as a solvent In the same manner as in Example 3, silyl ethers of various alcohols and 1 of various alcohols were used in ether with silicon tetrachloride and silver perchlorate as catalysts.
-O- (2- (2-methoxyethoxy) acetyl)-
The reaction of 2,3,4,6-tetra-O-benzyl-D-glucopyranose was performed (Formula 6), and the results shown in Table 4 were obtained.
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】[0016]
【表４】 [Table 4]
【００１７】（実施例６） １−Ｏ−（２−（２−メトキシエトキシ）アセチル）−
２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ−グルコピ
ラノースの合成 ２−（２ーメトキシエトキシ）酢酸（１．３４ｇ）にチ
オニルクロリド（20ミリリットル）を加え、１時間加熱
還流した。過剰のチオニルクロリドを減圧下留去した。
残渣にピリジン（２０ミリリットル）、２，３，４，６
−テトラ−Ｏ−ベンジル−Ｄ−グルコピラノース（５．
４１ｇ）のピリジン溶液（２０ミリリットル）を加え室
温で２時間攪拌した。得られた溶液を氷水に加え、塩化
メチレンで抽出した。有機層を２Ｎ塩酸で洗浄した後、
水洗し無水硫酸ナトリウムで乾燥した。溶媒を減圧下留
去し、シリカゲルクロマトグラフィーにて生成し、目的
の１−Ｏ−（２−（２−メトキシエトキシ）アセチル）
−２，３，４，６−テトラ−Ｏ−ベンジル−Ｄ−グルコ
ピラノースをアルファ体とベータ体の混合物として得
た。（５．２５ｇ、８０％）得られた混合物の異性体比
をＮＭＲスペクトルを用いて分析し、アルファ：ベータ
＝４：１であった。得られた混合物は、分離することな
くグリコシル化反応の供与体としてそのまま用いた。ま
た、得られた混合物をさらにシリカゲルカラムクロマト
グラフィーにて精密に分離し、アルファ体、ベータ体の
純粋物を得、ＮＭＲスペクトルにて構造を決定した。Ｎ
ＭＲ （２７０ＭＨｚ、ＣＤＣｌ3 、δ）Example 6 1-O- (2- (2-methoxyethoxy) acetyl)-
Synthesis of 2,3,4,6-tetra-O-benzyl-D-glucopyranose Thionyl chloride (20 ml) was added to 2- (2-methoxyethoxy) acetic acid (1.34 g), and the mixture was heated under reflux for 1 hr. Excess thionyl chloride was distilled off under reduced pressure.
Pyridine (20 ml), 2,3,4,6 in the residue
-Tetra-O-benzyl-D-glucopyranose (5.
41 g) of pyridine solution (20 ml) was added, and the mixture was stirred at room temperature for 2 hours. The resulting solution was added to ice water and extracted with methylene chloride. After washing the organic layer with 2N hydrochloric acid,
It was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and silica gel chromatography was performed to obtain the desired 1-O- (2- (2-methoxyethoxy) acetyl).
-2,3,4,6-Tetra-O-benzyl-D-glucopyranose was obtained as a mixture of an alpha form and a beta form. (5.25 g, 80%) The isomer ratio of the resulting mixture was analyzed using NMR spectrum and was alpha: beta = 4: 1. The resulting mixture was used as is as a donor for the glycosylation reaction without separation. Further, the obtained mixture was further precisely separated by silica gel column chromatography to obtain pure alpha-form and beta-form, and the structure was determined by NMR spectrum. N
MR (270MHz, CDCl 3 , δ)
【００１８】アルファ体：７．３４−７．１１（ｍ，２
０Ｈ）、６．４６（ｄ，１Ｈ，Ｊ＝３．３Ｈｚ），４．
９４（ｄ，１Ｈ，Ｊ＝１０．９Ｈｚ），４．８４（ｄ，
１Ｈ，Ｊ＝１０．６Ｈｚ），４．８１（ｄ，１Ｈ，Ｊ＝
１０．９Ｈｚ），４．７０（ｄ，１Ｈ，Ｊ＝１１．４Ｈ
ｚ），４．６３（ｄ，１Ｈ，Ｊ＝１１．４Ｈｚ），４．
５９（ｄ，１Ｈ，Ｊ＝１１．９Ｈｚ），４．５０（ｄ，
１Ｈ，Ｊ＝１０．６Ｈｚ），４．４６（ｄ，１Ｈ，Ｊ＝
１１．９Ｈｚ），４．２５（ｄ，１Ｈ，Ｊ＝１７．０Ｈ
ｚ），４．１７（ｄ，１Ｈ，Ｊ＝１７．０Ｈｚ），３．
９１（ｄｄ，１Ｈ，Ｊ＝９．１，９．２Ｈｚ），３．８
５（ｄｄ，１Ｈ，Ｊ＝１．９，１０．１Ｈｚ），３．７
４（ｄｄ，１Ｈ，Ｊ＝８．４，９．１Ｈｚ），３．７２
（ｔ，２Ｈ，Ｊ＝４．５Ｈｚ），３．６９（ｄｄ，１
Ｈ，Ｊ＝３．３， ９．２Ｈｚ），３．６８（ｄｄｄ，
１Ｈ，Ｊ＝１．７，１．９，８．４Ｈｚ），３．６６
（ｄｄ，１Ｈ，Ｊ＝１．７，１０．１Ｈｚ），３．５３
（ｔ，２Ｈ，Ｊ＝４．５Ｈｚ），３．５０（ｓ，３
Ｈ）．Alpha field: 7.34-7.11 (m, 2
0H), 6.46 (d, 1H, J = 3.3Hz), 4.
94 (d, 1H, J = 10.9 Hz), 4.84 (d,
1H, J = 10.6 Hz), 4.81 (d, 1H, J =
10.9Hz), 4.70 (d, 1H, J = 11.4H
z), 4.63 (d, 1H, J = 11.4 Hz), 4.
59 (d, 1H, J = 11.9 Hz), 4.50 (d,
1H, J = 10.6 Hz), 4.46 (d, 1H, J =
11.9 Hz), 4.25 (d, 1H, J = 17.0H
z), 4.17 (d, 1H, J = 17.0 Hz), 3.
91 (dd, 1H, J = 9.1, 9.2 Hz), 3.8
5 (dd, 1H, J = 1.9, 10.1 Hz), 3.7
4 (dd, 1H, J = 8.4, 9.1 Hz), 3.72
(T, 2H, J = 4.5 Hz), 3.69 (dd, 1
H, J = 3.3, 9.2 Hz), 3.68 (ddd,
1H, J = 1.7, 1.9, 8.4 Hz), 3.66
(Dd, 1H, J = 1.7, 10.1 Hz), 3.53
(T, 2H, J = 4.5Hz), 3.50 (s, 3
H).
【００１９】ベータ体：７．３３−７．１１（ｍ，２０
Ｈ）、５．６７（ｄ，１Ｈ，Ｊ＝７．９Ｈｚ），４．８
９（ｄ，１Ｈ，Ｊ＝１０．９Ｈｚ），４．８２（ｄ，１
Ｈ，Ｊ＝１１．２Ｈｚ），４．８１（ｄ，１Ｈ，Ｊ＝１
１．２Ｈｚ），４．８１（ｄ，１Ｈ，Ｊ＝１１．２Ｈ
ｚ），４．７８（ｄ，１Ｈ，Ｊ＝１１．２Ｈｚ），
４．７２（ｄ，１Ｈ，Ｊ＝１０．９Ｈｚ），４．７１
（ｄ，１Ｈ，Ｊ＝１１．２Ｈｚ），４．６１（ｄ，１
Ｈ，Ｊ＝１２．２Ｈｚ），４．１８（ｄ，１Ｈ，Ｊ＝１
７．２Ｈｚ），４．０３（ｄ，１Ｈ，Ｊ＝１７．２Ｈ
ｚ），３．７７（ｄｄ，１Ｈ，Ｊ＝３．８，１０．７Ｈ
ｚ），３．７４（ｄｄ，１Ｈ，Ｊ＝８．０，８．９Ｈ
ｚ），３．７１（ｄｄｄ，１Ｈ，Ｊ＝２．２，３．８，
８．９Ｈｚ），３．７１（ｄｄ，１Ｈ，Ｊ＝８．０，
８．３Ｈｚ），３．６８（ｔ，２Ｈ，Ｊ＝２．０Ｈ
ｚ），３．５９（ｄｄ，１Ｈ，Ｊ＝２．２，１０．７Ｈ
ｚ），３．５８（ｄｄ，１Ｈ，Ｊ＝７．９，８．３Ｈ
ｚ），３．５４（ｔ，２Ｈ，Ｊ＝２．０Ｈｚ），３．５
４（ｔ，２Ｈ，Ｊ＝４．５Ｈｚ），３．３５（ｓ，３
Ｈ）．Beta body: 7.33-7.11 (m, 20
H), 5.67 (d, 1H, J = 7.9 Hz), 4.8
9 (d, 1H, J = 10.9Hz), 4.82 (d, 1
H, J = 11.2 Hz, 4.81 (d, 1H, J = 1
1.2Hz), 4.81 (d, 1H, J = 11.2H
z), 4.78 (d, 1H, J = 11.2 Hz),
4.72 (d, 1H, J = 10.9 Hz), 4.71
(D, 1H, J = 11.2 Hz), 4.61 (d, 1
H, J = 12.2 Hz), 4.18 (d, 1H, J = 1
7.2 Hz), 4.03 (d, 1H, J = 17.2H
z), 3.77 (dd, 1H, J = 3.8, 10.7H)
z), 3.74 (dd, 1H, J = 8.0, 8.9H)
z), 3.71 (ddd, 1H, J = 2.2, 3.8,
8.9 Hz), 3.71 (dd, 1H, J = 8.0,
8.3 Hz), 3.68 (t, 2H, J = 2.0H
z), 3.59 (dd, 1H, J = 2.2, 10.7H
z), 3.58 (dd, 1H, J = 7.9, 8.3H
z), 3.54 (t, 2H, J = 2.0 Hz), 3.5
4 (t, 2H, J = 4.5 Hz), 3.35 (s, 3
H).
【００２０】[0020]
【発明の効果】本発明により、安定なグリコシル供与体
が提供されるとともに、少量の触媒でアルファ−Ｄ−グ
リコピラノシド誘導体もしくはベータ−Ｄ−グルコピラ
ノシド誘導体を、高い選択性で収率よく簡便に合成する
ことができる。INDUSTRIAL APPLICABILITY According to the present invention, a stable glycosyl donor is provided and an alpha-D-glycopyranoside derivative or a beta-D-glucopyranoside derivative can be easily synthesized with a high selectivity in a high yield with a small amount of catalyst. be able to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｈ 15/18 Ｃ０７Ｊ 17/00 9051−4Ｃ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07H 15/18 C07J 17/00 9051-4C // C07B 61/00 300
Claims (3)
ラ−Ｏ−アルキル−Ｄ−グリコピラノシドとアルコール
のトリメチルシリルエーテルを触媒量のルイス酸あるい
はルイス酸と過塩素酸銀またはトリフルオロメタンスル
ホン酸銀の混合触媒の存在下エーテル系溶媒中で反応さ
せることを特徴とするアルファ−Ｄ−グリコピラノシド
誘導体の合成方法。1. A catalytic amount of a trimethylsilyl ether of 1-O-acyl-2,3,4,6-tetra-O-alkyl-D-glycopyranoside and an alcohol as a Lewis acid or a Lewis acid and silver perchlorate or trifluoromethane. A method for synthesizing an alpha-D-glycopyranoside derivative, which comprises reacting in an ether solvent in the presence of a mixed catalyst of silver sulfonate.
ラ−Ｏ−アルキル−Ｄ−グリコピラノシドとアルコール
のトリメチルシリルエーテルを触媒量のルイス酸あるい
はルイス酸と過塩素酸銀またはトリフルオロメタンスル
ホン酸銀の混合触媒の存在下芳香族系溶媒、塩素系溶媒
もしくはニトロメタン、アセトニトリル溶媒中で反応さ
せることを特徴とするベータ−Ｄ−グリコピラノシド誘
導体の合成方法。2. A catalytic amount of a trimethylsilyl ether of 1-O-acyl-2,3,4,6-tetra-O-alkyl-D-glycopyranoside and an alcohol as a Lewis acid or a Lewis acid and silver perchlorate or trifluoromethane. A method for synthesizing a beta-D-glycopyranoside derivative, which comprises reacting in an aromatic solvent, a chlorine solvent or a nitromethane or acetonitrile solvent in the presence of a silver sulfonate mixed catalyst.
トキシベンジル、３，４−ジメトキシベンジル、２，４
−ジメトキシベンジル、パラクロロベンジル、メタクロ
ロベンジル、３，４−ジクロロベンジル、２，４−ジク
ロロベンジルを表す。）で示される化合物。3. The following chemical formula 1 or chemical formula 2 [Chemical 2] (In the formula, R is benzyl, paramethoxybenzyl, metamethoxybenzyl, 3,4-dimethoxybenzyl, 2,4
Represents dimethoxybenzyl, parachlorobenzyl, metachlorobenzyl, 3,4-dichlorobenzyl, 2,4-dichlorobenzyl. ) The compound shown by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5203733A JPH0733792A (en) | 1993-07-27 | 1993-07-27 | New glycosyl donor and method of glycosylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5203733A JPH0733792A (en) | 1993-07-27 | 1993-07-27 | New glycosyl donor and method of glycosylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0733792A true JPH0733792A (en) | 1995-02-03 |
Family
ID=16478962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5203733A Withdrawn JPH0733792A (en) | 1993-07-27 | 1993-07-27 | New glycosyl donor and method of glycosylation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733792A (en) |
-
1993
- 1993-07-27 JP JP5203733A patent/JPH0733792A/en not_active Withdrawn
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| A300 | Withdrawal of application because of no request for examination |
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