3-O-Acetyl-4,6-di-O-benzyl-D-galactal | 81928-96-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-O-Acetyl-4,6-di-O-benzyl-D-galactal
• 英文别名: [(2R,3R,4R)-3-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-4-yl] acetate
• CAS: 81928-96-3
• 化学式: C₂₂H₂₄O₅
• 分子量: 368.43
• InChiKey: CHPILQYHQVGLCA-YPAWHYETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-O-Acetyl-4,6-di-O-benzyl-D-galactal 在 sodium tetrahydroborate 、 sodium azide 、 ammonium cerium(IV) nitrate 、 nickel dichloride 作用下， 以 乙醇 、 乙腈 为溶剂， 反应 31.33h， 生成 dimethylthexylsilyl 3-O-acetyl-4,6-di-O-benzyl-2-deoxy-2-trichloroacetamido-β-D-galactopyranoside
  参考文献：
  名称：

  Linear Synthesis of the Tumor-Associated Carbohydrate Antigens Globo-H, SSEA-3, and Gb3

  摘要：

  The tumor-associated carbohydrate antigens Globo-H, SSEA-3, and Gb3 were synthesized in a linear fashion using glycosyl phosphate monosaccharide building blocks. All of the building blocks were prepared from readily available common precursors. The difficult alpha-(1-->4-cis)-galactosidic linkage was installed using a galactosyl phosphate donor with high selectivity. Introduction of the beta-galactosamine unit required the screening a variety of amine protecting groups to ensure good donor reactivity and protecting group compatibility. An N-trichloroacetyl-protected galactosamine donor performed best for the installation of the beta-glycosidic linkage. Conversion of the trichloroacetyl group to the N-acetyl group was achieved under mild conditions, fully compatible with the presence of multiple glycosidic bonds. This synthetic strategy is expected to be amenable to the synthesis of the globo-series of tumor antigens on solid-support.

  DOI：

  10.1021/jo025834+
• 作为产物：
  描述：

  溴甲苯 在 吡啶 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 7.0h， 生成 3-O-Acetyl-4,6-di-O-benzyl-D-galactal
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157

文献信息

• Iridium-promoted deoxyglycoside synthesis: stereoselectivity and mechanistic insight
  作者：Kumar Bhaskar Pal、Aoxin Guo、Mrinmoy Das、Jiande Lee、Gábor Báti、Benjamin Rui Peng Yip、Teck-Peng Loh、Xue-Wei Liu

  DOI：10.1039/d0sc06529c

  日期：——

  devised a method for stereoselective O-glycosylation using an Ir(I)-catalyst which enables both hydroalkoxylation and nucleophilic substitution of glycals with varying substituents at the C3 position. In this transformation, 2-deoxy-α-O-glycosides were acquired when glycals equipped with a notoriously poor leaving group at C3 were used; in contrast 2,3-unsaturated-α-O-glycosides were produced from glycals

  在本文中，我们设计了一种使用Ir（I）催化剂进行立体选择性O-糖基化的方法，该方法能够在C3位置使用不同的取代基进行糖的加氢烷氧基化和亲核取代。在该转化中，当使用在C3处带有一个臭名昭著的离去基团的糖时，获得了2-脱氧-α- O-糖苷。相反，由在C3具有良好离去基团的糖基产生2，3-不饱和-α - O-糖苷。机制研究表明，这两个反应进行经由所述引导机构，通过其受体坐标到IR（我在α-面配位Ir）的金属（我）-糖基π-复合物，然后以顺式加成方式攻击包含O-糖苷键的糖基。该方案表现出良好的官能团耐受性，并以中等至高收率和优异的立体选择性制备寡糖文库为例。
• Palladium(<scp>ii</scp>)-catalyzed stereoselective synthesis of <i>C</i>-glycosides from glycals with diaryliodonium salts
  作者：Kumar Bhaskar Pal、Jiande Lee、Mrinmoy Das、Xue-Wei Liu

  DOI：10.1039/d0ob00247j

  日期：——

  An efficient palladium(II) mediated C-glycosylation of glycals with diaryliodonium salts is described, providing a new strategy for the synthesis of 2,3-dideoxy C-aryl glycosides with excellent stereoselectivity. The C-glycosylation of a diverse range of glycals, including D-glucal, D-galactal, D-allal, L-rhamnal, L-fucal, L-arabinal, D-maltal, and D-lactal, occurred effectively and the corresponding

  描述了有效的钯（II）介导的二芳基碘鎓盐对糖的C-糖基化，为合成具有优异立体选择性的2,3-二脱氧C-芳基糖苷提供了新的策略。所述Ç不同范围的烯糖的-glycosylation，包括d -glucal，d -galactal，d -allal，大号-rhamnal，大号-fucal，大号-arabinal，d -maltal，和d -lactal，有效地发生，并且相应的C-β-糖苷以中等至良好的产率获得。由于丰富的官能团相容性，广泛的底物范围和出色的α-立体选择性，该方案被认为是对碳水化合物化学领域的重要补充。
• Different reaction routes found in acid-catalyzed glycosylation of endo- and exo-glycals: competition between Ferrier rearrangement and protonation
  作者：Hui-Chang Lin、Wen-Ping Du、Chih-Chun Chang、Chun-Hung Lin

  DOI：10.1016/j.tetlet.2005.05.061

  日期：2005.7

  products is often obtained resulting from Ferrier rearrangement and protonation. The former reaction exclusively takes place with the t-butyl carbonate or hydroxyl substituent at the C3 position of endo-glycals, while the latter mainly occurs in the glycosylation of exo-glycals with allyl benzyl ether or acetate. In addition to the substituent effect, protecting groups are critical to determine the

  内-和外-糖的酸介导的糖基化已经以良好或优异的产率进行，其中经常由于费里耳重排和质子化而获得两种产物的混合物。前者反应只发生与吨丁基碳酸酯或在C3位羟基取代基内切-glycals，而后者主要发生在糖基化外型-glycals与烯丙基苄基醚或乙酸盐。除取代基作用外，保护基对于确定活性和有利的反应途径也至关重要。此外，该方法适用于O-，C-和N-亲核试剂。
• Synthesis of <scp>2‐Amino</scp>‐2‐deoxy‐1,3‐dithioidoglycosides <i>via</i> Organocatalytic Relay Glycosylation of <scp>3‐<i>O</i>‐Acetyl</scp>‐2‐nitrogalactals
  作者：Yongyong Wan、Lei Deng、Liming Wang、Yuanhong Tu、Hui Liu、Jian‐song Sun、Qingju Zhang

  DOI：10.1002/cjoc.202300307

  日期：2023.11

  drugs. Thioglycosides have enhanced stability for acid-mediated or enzymatic hydrolysis, and have a wide range of applications in glycobiology and drug development. Herein, we describe an efficient method for site-selective and stereoselective synthesis of potential bioactive 2-amino-2-deoxy-1,3-dithioidoglycosides via organocatalysis sequential C3-Ferrier rearrangement and Michael addition of 3-O

  艾糖型苷类具有多种生物活性，已广泛用作抗凝血药物和抗感染药物。硫代糖苷增强了酸介导或酶水解的稳定性，在糖生物学和药物开发中具有广泛的应用。在此，我们描述了一种通过有机催化连续 C3-Ferrier 重排和 3- O迈克尔加成，位点选择性和立体选择性合成潜在生物活性 2-氨基-2-脱氧-1,3-二硫代糖苷的有效方法。-乙酰基-2-硝基半乳糖。分步方案和一锅法方案均已实施且效果良好。这种独特的硫代糖基化方案突出了各种优点，包括（i）反应条件温和；(ii) 优异的位点选择性和立体选择性，产率良好至优异；(iii) 底物范围广泛；(iv) 原子经济且环境友好；(v) 反应可以扩大规模。
• Stereoselective glycosylation of endo-glycals by microwave- and AlCl3-assisted catalysis
  作者：Hui-Chang Lin、Jia-Fu Pan、Yen-Bo Chen、Zi-Ping Lin、Chun-Hung Lin

  DOI：10.1016/j.tet.2011.05.124

  日期：2011.8

  alpha-2-Deoxyglycosides were synthesized in good to excellent yields by microwave-assisted reaction of endo-glycals with various O-nucleophiles in the presence of catalytic amount of AlCl3. These glycosyl additions occurred with high alpha-stereoselectivity and were complete in 5-35 min in 65-93% yield. (C) 2011 Elsevier Ltd. All rights reserved.