phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-fucopyranoside | 196397-53-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-fucopyranoside
• 英文别名: [(2S,3R,4R,5S,6S)-4,5-diacetyloxy-2-methyl-6-phenylsulfanyloxan-3-yl] acetate
• CAS: 196397-53-2
• 化学式: C₁₈H₂₂O₇S
• 分子量: 382.434
• InChiKey: YPJGKQRQWRZEKO-RSRHVSAYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-fucopyranoside 在 palladium on activated charcoal 、 Lindlar's catalyst 、 palladium on calcium fluoride poisoned with lead 甲醇 、 4-二甲氨基吡啶 、 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸酐 、 水 、 氢气 、 mercury(II) trifluoroacetate 、 四丁基碘化铵 、 sodium hydride 、 potassium carbonate 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -78.0~60.0 ℃ 、101.33 kPa 条件下， 反应 35.17h， 生成 methyl (2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1->4)-(2,3,4-tri-O-acetyl-α-L-fucopyranosyl)-(1->3)-6-O-acetyl-2-acetamido-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  推广糖基化：使用一组标准反应条件合成血型抗原 Lea、Leb 和 Lex

  摘要：

  由于任何糖基化方法都没有通用的反应条件，因此世界上只有少数实验室才能制造出具有生物学意义的寡糖。为了让非专业人士也能合成碳水化合物，关键是要有一种糖基化方法，可以在单一条件下在多种情况下发挥作用。由于结构复杂，Lewis 血型抗原引起了许多合成碳水化合物组的注意。尽管它们已被多次合成，但从未在一组反应条件下使用单一糖基化方法制备它们。在本文中，我们表明亚砜糖基化方法可用于形成路易斯血型抗原 Lea (1)、Leb (2)、和 Lex (3) 在一组统一的反应条件下立体选择性地进行。这项工作突出了亚砜方法的灵活性，并证明了其在构建相关族中的效用...

  DOI：

  10.1021/ja9608555
• 作为产物：
  描述：

  6-deoxy-L-galactose 在 吡啶 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 生成 phenyl 2,3,4-tri-O-acetyl-1-thio-α-L-fucopyranoside
  参考文献：
  名称：

  Gram-Scale Synthesis of an Armed Colitose Thioglycoside

  摘要：

  A concise gram-scale synthesis of protected colitose thioglycosides for use in bacterial carbohydrate antigen synthesis is described. The synthesis proceeds in six steps and 59-70% overall yield from commercially available l-fucose, making it the most efficient route reported to date. Key steps include regioselective installation of a thiocarbonate using catalytic dioctyltin dichloride (10 mol%) and a tris(trimethylsilyl)silane-mediated radical deoxygenation.

  DOI：

  10.1021/jo501472v

文献信息

• Acylation of carbohydrates over Al2O3: preparation of partially and fully acylated carbohydrate derivatives and acetylated glycosyl chlorides
  作者：Pallavi Tiwari、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.11.035

  日期：2006.2

  protocol does not require the addition of any base or activator. This methodology has been further extended to the selective acylation of carbohydrate diols and the one-pot preparation of acetylated glycosyl chlorides direct from free reducing sugars. The yields obtained in most of the cases are excellent.

  据报道，使用酰氯和固体支持剂Al2O3对碳水化合物衍生物进行选择性和全O酰化。该协议不需要添加任何碱或活化剂。该方法已经进一步扩展到碳水化合物二醇的选择性酰化和直接从游离还原糖直接制备一锅乙酰化糖基氯的方法。在大多数情况下所获得的产量是极好的。
• Direct one-pot conversion of acylated carbohydrates into their alkylated derivatives under heterogeneous reaction conditions using solid NaOH and a phase transfer catalyst
  作者：Soni Kamlesh Madhusudan、Geetanjali Agnihotri、Devendra S. Negi、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.03.007

  日期：2005.5

  A convenient one-pot protocol for the direct conversion of acyl-protected carbohydrates into their alkylated counterparts has been developed by using alkyl halides in the presence of solid sodium hydroxide and a phase transfer catalyst. These economically convenient, mild, two-phase reaction conditions allow the preparation of a variety of monosaccharide intermediates for use in the synthesis of complex

  通过在固体氢氧化钠和相转移催化剂存在下使用烷基卤，已经开发了一种方便的一锅法方案，用于将酰基保护的碳水化合物直接转化为其烷基化的对应物。这些经济上方便，温和的两相反应条件允许制备用于合成复杂寡糖的各种单糖中间体。
• Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga <i>Polycavernosa</i> <i>tsudai</i>
  作者：Leo A. Paquette、Louis Barriault、Dmitri Pissarnitski、Jeffrey N. Johnston

  DOI：10.1021/ja993487o

  日期：2000.2.1

  A stereoselective total synthesis of natural levorotatory polycavemoside A (1) has been achieved. initial investigations produced the properly activated disaccharide unit 18b via the conjoining of building blocks originating from L-fucose and D-xylose. This objective was followed by preparation of the phenylsulfonyl-substituted tetrahydropyran 23 and aldehyde 30. After proper linking of these key compounds, important information had to be garnered on the sequence of steps that would ultimately result in successful access to 1. Although oxidation to generate alpha-diketone 35 and unmasking of the C-13 hydroxyl did give rise efficiently to lactol 36, this functionality did not pave the way for ensuring macrolactonization. When this sequence of steps was reversed, it was indeed possible to arrive at the heavily functionalized precursor 43. However, numerous experiments failed to result in the requisite activation of C-16 for attachment of the trienyl side chain. However, if the E-vinyl iodide was elaborated in advance of alpha-diketone generation, glycosidation, and complete side chain construction, arrival at 1 proceeded without unsurmountable complications to furnish the targeted marine toxin.
• Synthesis of fully protected α-l-fucopyranosyl-(1→2)-β-d-galactopyranosides with a single free hydroxy group at position 2′, 3′ or 4′ using O-(2-naphthyl)methyl (NAP) ether as a temporary protecting group
  作者：Zoltán B. Szabó、Anikó Borbás、István Bajza、András Lipták

  DOI：10.1016/j.tetasy.2004.11.056

  日期：2005.1

  Perbenzylated methyl alpha-L-fucopyranosyl-(1-->2)-beta-D-galactopyranosides having a single free OH group at position C-2'. C-3' or C-4' have been synthesized. Methyl 3,4,6-tri-O-benzyl-beta-D-galactopyranoside was glyco-sylated either with phenyl 3,4-di-O-benzyl-2-O-(2-naphthyl)-methyl-, phenyl 2,4-di-O-benzyl-3-O-(2-naphthyl)methyl- or phenyl 2,3-di-O-benzyl-4-O-(2-naphthyl)methyl-1-thio-beta-L-fucopyranoside. The 2-ONAP ether functioned well as a non-participating group. The yields of the glycosylation reactions, promoted by NIS/TfOH, were above 80% and the stereoselectivity was 8:1 to 10:1 in favour of the alpha-anomers. The 2-ONAP ether was obtained by (2-naphthyl)methylation, the 3-ONAP and the 4-ONAP ethers were prepared either by hydrogenolysis of the 3,4-O-(2-naphthyl)methylene acetals of beta-L-fucopyranoside or by tin acetal-mediated alkylations. The latter procedure afforded higher yields. The ONAP ethers from the disaccharides were removed by oxidative cleavage with DDQ. (C) 2004 Elsevier Ltd. All rights reserved.
• Concise Synthesis of 1-Thioalkyl Glycoside Donors by Reaction of Per-O-acetylated Sugars with Sodium Alkanethiolates under Solvent-Free Conditions
  作者：Guang-Jing Feng、Tao Luo、Yang-Fan Guo、Chun-Yang Liu、Hai Dong

  DOI：10.1021/acs.joc.1c02171

  日期：2022.3.4