Catalytic Stereoselective Synthesis of Glycosides

糖苷的催化立体选择性合成

• 批准号: 06453065
• 负责人: MUKAIYAMA Teruaki
• 金额: $ 5.31万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453065/
• 关键词: Stereoselective Synthesis; Glyuosides; Glucopyranosides; Galactopyranosides; Trisethylsilyl Ethers; Amiuopyuarosides; N-Glycosides; Ribosides; シアル酸; α-グリコシド; 二価スズトリフラート; イッテルビウムトリフラート; ランタントリフラート; ヘキサメチルジシロキサン; リボース; β-リボシド; 塩化スズ(II); ノ-ヒ

In the presence of a catalytic amount of tin (II) trifluoromethanesulfonate or ytterbium (III) trifluoromethanesulfonate, various 2-amino-beta-D-glucopyranosides or galactopyranosides are stereoselectively synthesized in high yields from 1, 3, 4, 6-tetra-O-acetyl-2- (2, 2, 2-trichloroethoxy-carbonylamino) -2-deoxy-beta-D-glucopyranose and galactopyranose or 1, 3, 4, 6-tetra-O-acetyl-2-allyloxycarbonylamino-2-deoxy-beta-D-glucopyranose on treatment with alkyl trimethylsilyl ethers or free alcohols.Further, 2-amino-alpha-D-glucopyranosides or galactopyranosides are respectively prepared in high yields with almost perfect stereoselections from the same glycosyl donors using a catalyst generated from tin (IV) chloride and a silver salt via an anomerization step.In the coexistence of hexamethyldisiloxane and anhydrous calcium sulfate, a catalytic amount of an activator such as tin (II) trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate or tin (II) chloride smoothly promotes the glycosylation reactions between 1-hydroxy sugars and free alcohols, electron-rich aromatic compounds or silylated uncleophiles to produce various O-, C- or N-beta-glycosides stereoselectively in high yields whereas alpha-ribosides are obtained predominantly by the further addition of lithium perchlorate. In the case of carbon nucleophiles such as electron-rich aromatic compounds or silyl enol ethers derived from carbonyl compounds, perfect beta-selectivity is shown either in the presence or absence of lithium perchlorate.

在催化量的三氟甲烷磺酸锡或三氟甲烷磺酸镱存在下，以1,3,4,6 -四- o-乙酰基-2-（2,2,2 -三氯乙氧基-羰基氨基）-2-脱氧- β -d -葡萄糖吡喃糖和半乳糖吡喃糖或1,3,4为原料立体选择性地高收率合成了各种2-氨基- β -d -葡萄糖吡喃苷或半乳糖吡喃苷。6-四- o-乙酰基-2-烯丙氧羰基氨基-2-脱氧-d -葡萄糖吡喃糖用烷基三甲基硅醚或游离醇处理。此外，使用由氯化锡和银盐通过异构化步骤生成的催化剂，以相同的糖基供体分别以高收率和几乎完美的立体选择制备了2-氨基- α - d -葡萄糖吡喃苷或半乳糖吡喃苷。在六甲基二硅氧烷和无水硫酸钙共存的情况下，催化量的活化剂如三氟甲烷磺酸锡（II）、三氟甲烷磺酸镱、三氟甲烷磺酸镧或氯化锡（II）等能平稳地促进1-羟基糖与游离醇、富电子芳香化合物或硅基化亲叔络合物之间的糖基化反应，生成各种O-；C-或n -糖苷立体选择性产率高，而α -核糖苷主要通过进一步添加高氯酸锂获得。在碳亲核试剂的情况下，如富电子芳香化合物或从羰基化合物衍生的硅烯醇醚，在高氯酸锂存在或不存在的情况下都表现出完美的-选择性。

项目成果

Teruaki MUKAIYAMA, Koki MATSUBARA, and Miyuki HORA: "An Efficient Glycosylation Reaction of Hydroxy Sugars with Various Nucleophiles Using a Catalytic Amount of Activator and Hexamethyldisiloxane" Synthesis. 1994. 1368-1373

Teruaki MUKAIYAMA、Koki MATSUBARA 和 Miyuki HORA：“使用催化量的活化剂和六甲基二硅氧烷进行羟基糖与各种亲核试剂的高效糖基化反应”合成。

下村 直之: "Stereoselective Syntheses of B-D-Riborucleosides Catalyzed" Bull.Chem.Soc.Jpn.67. 3100-3106 (1994)

Naoyuki Shimomura：“催化 B-D-核糖核苷的立体选择性合成”Bull.Chem.Soc.Jpn.67 (1994)。

Naoyuki SHIMOMURA: "Tin (II) Chloride Catalyzed Synthesis of β-D-Ribonucleosides" Chemistry Letters. 2089-2092 (1994)

Naoyuki Shimomura：“氯化锡催化 β-D-核糖核苷的合成”化学快报 2089-2092 (1994)。

Naoyuki SHIMOMURA, Takafumi MATSUTANI, and Teruaki MUKAIYAMA: "Stereoselective Syntheses of beta-D-Ribonucleosides Catalyzed by the Combined Use of Silver Salts and Diphenyltin Sulf? Y30 Lawesson's Reagent" Bull. Chem. Soc. Jpn.67. 3100-3106 (1994)

Naoyuki SHIMOMURA、Takafumi MATSUTANI 和 Teruaki MUKAIYAMA：“联合使用银盐和二苯基锡磺催化的 β-D-核糖核苷的立体选择性合成？Y30 Lawesson 试剂”公牛。

Masashi Nagai: "Synthesis of N^6,2′,3′,5′-Tetrabenzoyl-β-D-adenosine Catalyzed by Metal Iodides" Heterocycles. 42. 57-63 (1996)

Masashi Nagai：“金属碘化物催化的 N^6,2′,3′,5′-四苯甲酰基-β-D-腺苷的合成”杂环化合物。 42. 57-63 (1996)