allyl 3,4,6-tri-O-acetyl-β-D-galactopyranoside | 152772-84-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 3,4,6-tri-O-acetyl-β-D-galactopyranoside
• 英文别名: [(2R,3S,4R,5R,6R)-3,4-diacetyloxy-5-hydroxy-6-prop-2-enoxyoxan-2-yl]methyl acetate
• CAS: 152772-84-4
• 化学式: C₁₅H₂₂O₉
• 分子量: 346.334
• InChiKey: UUISTBCDQWJVNT-UXXRCYHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  118
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  allyl 3,4,6-tri-O-acetyl-β-D-galactopyranoside 在 三氟甲磺酸三甲基硅酯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 palladium dichloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.67h， 生成 2-O-(2,2-dimethyl-2-(ortho-nitrophenyl)acetyl)-3,4,6-tri-O-acetyl-α-D-galactopyranosyl trichloroacetimidate
  参考文献：
  名称：

  双重参与保护基团解决了糖基化反应中的端基立体控制问题。

  摘要：

  2,2-二甲基-2-（邻-硝基苯基）乙酰基（DMNPA）基团可通过强大的邻近基团参与（NGP）或长距离参与（LDP）效应实现立体控制的1,2-反式，1,2-顺式，以及β-2,6-二脱氧糖苷键的生成，同时抑制了不希望的原酸酯副产物的形成。DMNPA强大的立体控制能力归因于酯官能团和硝基的双重参与作用，这已通过对照反应和DFT计算得到证实，并通过X射线光谱法得到进一步证实。

  DOI：

  10.1021/acs.orglett.9b03321
• 作为产物：
  描述：

  allyl 3,4,6-tri-O-acetyl-2-O-(2-chloroacetyl)-β-D-galactopyranoside 在 乙酸肼 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 5.0h， 以82%的产率得到allyl 3,4,6-tri-O-acetyl-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of 5-Thio-l-fucose-Containing Disaccharides, as Sequence-Specific Inhibitors, and 2‘-Fucosyllactose, as a Substrate of α-l-Fucosidases

  摘要：

  Four 5-thio-L-fucose-containing disaccharides having alpha(1-->6), alpha(1-->3), alpha(1-->4)GlcNAc, and alpha(1-->2-Gal linkages (compounds 1-4, respectively) were synthesized as potential alpha-L-fucosidase inhibitors. The glycosylation reactions using 2,3,4-tri-O-acetyl-5-thio-L-fucopyranosyl trichloroacetimidate as a glycosyl donor and BF3 . OEt(2) as a catalyst gave mainly alpha-linked disaccharides. Only alpha(1-->2)-linked disaccharide 4 showed inhibitory activity (K-i = 0.21 mM) against Bacillus alpha-L-fucosidase which hydrolyzes the Fuc alpha(1-->2) linkage specifically. The results suggested that sequence specificity of an enzyme could be estimated from the inhibitory activities of the compounds 1-4. In contrast, every disaccharide showed inhibitory activity (K-i = 30-91 mu M) against bovine epididymis alpha-L-fucosidase.

  DOI：

  10.1021/jo961725h

文献信息

• A Study on Stereoselective Glycosylations via Sulfonium Ion Intermediates
  作者：Rens A. Mensink、Hidde Elferink、Paul B. White、Nathalie Pers、Floris P. J. T. Rutjes、Thomas J. Boltje

  DOI：10.1002/ejoc.201600898

  日期：2016.9

  The stereoselective synthesis of 1,2-cis-linkages can be achieved by an Sn2-like displacement of glycosylation intermediates such as glycosyl triflates and sulfonium ions, provided that they display the right combination of stability and reactivity. Herein, we report the use of an achiral auxiliary that can impose neighboring group participation to afford glycosyl sulfonium ions, aided by the Thorpe–Ingold

  1,2-顺式键的立体选择性合成可以通过糖基化中间体（如糖基三氟甲磺酸酯和锍离子）的 Sn2 样置换来实现，前提是它们显示出稳定性和反应性的正确组合。在此，我们报告了在索普-英戈尔德效应的帮助下，使用非手性助剂可以强制相邻基团参与以提供糖基锍离子。我们研究了锍离子的糖基化特性，并使用变温 NMR (VT-NMR) 研究来研究它们在糖基化机制中的作用。研究了助剂结构、保护基团和糖基供体的立体化学的影响，并导致鉴定了高度α-选择性的半乳糖供体。
• BiBr₃-Promoted Activation of Peracetylated Glycosyl Iodides: Straightforward Access to Synthetically Useful 2-<i>O</i>-Deprotected Allyl Glycosides
  作者：Antonello Pastore、Matteo Adinolfi、Alfonso Iadonisi

  DOI：10.1002/ejoc.200800914

  日期：2008.12

  anomeric activation of acetylated glycosyl iodides. This reactivity can be exploited for straightforward access to allyl glycosides unprotected at the O-2 position. The reported protocol appears to be convenient in comparison with the pre-existing ones in that shorter experimental times are needed and the use of strong acids is avoided. Suitable structural features of substrates (6-deoxy sugars or use

  亚化学计量量的 BiBr3 能够促进乙酰化糖基碘的异头活化。这种反应性可用于直接获得在 O-2 位置未受保护的烯丙基糖苷。与先前存在的协议相比，报告的协议似乎很方便，因为需要更短的实验时间并且避免使用强酸。底物的合适结构特征（6-脱氧糖或使用苯甲酰基或甲氧基羰基 2-O 参与基团）将过程切换到优先糖苷化，而不会在 O-2 位置脱保护。（© Wiley-VCH Verlag GmbH & Co. KGaA , 69451 德国魏因海姆, 2008)
• Efficient and stereoselective 1,2-cis glycoside formation of 5-thioaldopyranoses: glycosylation with peracetylated 5-thio-D- arabinopyranosyl and 5-thio-L-fucopyranosyl trichloroacetimidates
  作者：Hironobu Hashimoto、Masayuki Izumi

  DOI：10.1016/s0040-4039(00)74054-8

  日期：1993.7

  Trichloroacetimidate method was proved to be effective for 5-thio-D-arabinopyranosylation and 5-thio-L-fucopyranosylation of N-acetyl-D-glucosaminides and D-galactosides. In these 5-thioglycosylation the neighboring group participation of 2-0-acetyl function was not decisive of anomeric stereoselectivity to give 1,2-cis pseudodisaccharides predominantly. Allyl 2-O-(5-thio-alpha-L-fucopyranosyl)-beta-D-galactopyranoside showed potent inhibitory activity toward alpha-L-fucosidase (Ki = 30muM).