allyl α-D-galactofuranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl α-D-galactofuranoside
• 英文别名: (2S,3R,4R,5S)-2-[(1R)-1,2-dihydroxyethyl]-5-prop-2-enoxyoxolane-3,4-diol
• 化学式: C₉H₁₆O₆
• 分子量: 220.222
• InChiKey: ZOIPKVBHIUBYNB-HXLXBVJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  99.4
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  allyl α-D-galactofuranoside 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 sodium methylate 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 palladium dichloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 16.84h， 生成 O-(2,6-di-O-benzyl-3,5-O-(di-tert-butylsilanediyl)-β-D-galactofuranosyl)trichloroacetimidate
  参考文献：
  名称：

  Glycosylation studies on conformationally restricted 3,5-O-(di-tert-butylsilylene)-d-galactofuranosyl trichloroacetimidate donors for 1,2-cis α-d-galactofuranosylation

  摘要：

  Conformationally restricted 3,5-O-di-tert-butylsilylene-D-galactofuranosyl trichloroacetimidate donors were synthesized from allyl alpha-D-galactofuranoside for the construction of 1,2-cis alpha-D-galactofuranosyl linkages. Glycosylation reactions were performed with several acceptors, including D-galactono-1,4-lactone, D-rhamnopyranosyl, and D-mannopyranosyl derivatives. The influence of the temperature and the reaction solvents was evaluated, as well as the 6-O-substitution pattern of the donor. The higher alpha-selectivities were obtained at -78 degrees C in diethyl ether as solvent. 6-O-Acetyl substitution on constrained donor increased the alpha-selectivity compared to the 6-O-benzyl substitution. Almost no selectivities were observed in the non-participating solvent CH2Cl2. In contrast, ethereal solvents enhanced the alpha-selectivity suggesting a participating effect in the reaction intermediate. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2011.10.004
• 作为产物：
  描述：

  D-吡喃葡萄糖 、 3-溴丙烯 在 N,N-二甲基丙烯基脲 、 sodium hydride 作用下， 以 mineral oil 为溶剂， 反应 72.0h， 以60%的产率得到allyl α-D-galactofuranoside
  参考文献：
  名称：

  Synthesis of glycoimmunogen Tn-Thr-PS A1 via hydrazone bond and stability optimization of PS A1 monosaccharide mimics under vaccine development conditions

  摘要：

  Previously, our group constructed several immunogens utilizing oxime linkage to conjugate a T-cell stimulatory zwitterionic polysaccharide PS A1 and tumor associated carbohydrate antigens (TACAs) in acetate buffer. Here, a semi-synthetic immunogen was synthesized using hydrazone conjugation between PS A1 and a glycopeptide hydrazide (alpha-D-GalNAc-L-Thr-NH-NH2) with an excellent loading in PBS buffer. To get robust immune response, the retention of zwitterionic character of PS A1 under vaccine construction conditions is essential. In this regard, the stability of embedded pyruvate acetal moiety in tetrasaccharide repeating unit of PS A1 can validate the retention of the dual charges. Therefore, rather than utilizing this highly immunogenic PS A1 fully, stability studies were performed with synthetic 1-thiophenyl-4,6-O-pyruvate acetal-D-galactopyranose in varying acetate buffer pHs and time intervals. Furthermore, 1-propyl-D-galactofuranose was synthesized to mimick the D-Galf of PS A1 to examine regioselective hydrazone and oxime formation with alpha-D-GalNAc-L-Thr-NH-NH2 and alpha-D-GalNAc-ONH2 moieties respectively.

  DOI：

  10.1080/07328303.2019.1709975

文献信息

• Synthesis of α-<scp>d</scp>-Glcp-(1→3)-α-<scp>d</scp>-Galf-(1→2)-α-<scp>l</scp>-Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-<scp>d</scp>-galactofuranosylation
  作者：Gabriel Gola、Carola Gallo-Rodriguez

  DOI：10.1039/c3ra45658g

  日期：——

  The synthesis of the trisaccharide α-D-Glcp-(1→3)-α-D-Galf-(1→2)-L-Rhap (3) constituent of Streptococcus pneumonia 22F was achieved with complete diastereoselectivity. This is the first example of a synthesis of an internal α-D-Galf containing oligosaccharide of a pathogen microorganism. Allyl α-D-galactofuranoside, used as novel precursor of the internal Galf, allowed the introduction of an orthogonal group at O-3. The trichloroacetimidate method was used for the construction of 1,2-cis-α-D-galactofuranosyl linkage. The influence of the 3-O-substituent (PMB, Bz, PFBz, PMBz, TIPS) was evaluated in benzylated galactofuranosyl trichloroacetimidate donors in terms of yield and selectivity of α-D-Galf-(1→2)-α-L-Rhap product as well as donor rearrangement by-product. Complete stereoselectivity was observed with all protecting groups used in the Galf donor, but the 3-O-benzoyl substitution gave the best yield. Protective groups were also evaluated in the rhamnoside acceptor, benzyl substitution was a requirement for complete stereoselectivity.

  以完全非对映选择性合成了肺炎链球菌 22F 的三糖δ±-D-Glcp-(1â3)-δ±-D-Galf-(1â2)-L-Rhap (3)。这是首次合成病原微生物内部含有δ-D-Galf 的寡糖。使用烯丙基δ±-D-半乳糖呋喃糖苷作为内部 Galf 的新型前体，可以在 O-3 处引入一个正交基团。三氯乙酰亚氨酸法用于构建 1,2-顺式-δ±-D-半乳糖呋喃糖基连接。根据δ-D-Galf-(1â2)-δ-L-Rhap 产物以及供体重排副产物的产量和选择性，评估了苄基半乳糖呋喃糖基三氯乙酰亚胺供体中 3-O 取代基（PMB、Bz、PFBz、PMBz、TIPS）的影响。在 Galf 供体中使用的所有保护基团都具有完全的立体选择性，但 3-O 苯甲酰基取代的产率最高。还对鼠李糖苷受体中的保护基团进行了评估，发现苄基取代是完全立体选择性的必要条件。
• Klotz, Wolfgang; Schmidt, Richard R., Liebigs Annalen der Chemie, 1993, # 6, p. 683 - 690
  作者：Klotz, Wolfgang、Schmidt, Richard R.

  DOI：——

  日期：——
• Kinetic Products Under Thermal Conditions: Rapid Entry into α/β-D-Galactofuranosides Using Microwave Irradiation and Selective Lewis Acids
  作者：Soumava Santra、Emily Jonas、Jean-Paul Bourgault、Tarick El-Baba、Peter R. Andreana

  DOI：10.1080/07328303.2011.585259

  日期：2011.1.1

  A modified Fischer-Lubineau reaction, employing microwave irradiation and selected Lewis acids such as Mn(ClO4)(2), Mn(C2H3O2)(3), FeCl3, CoCl2, and AgF as independent additives, induces rapid entry into alpha/beta-D-galactofuranosides in very good yield and purity.
• Synthesis of glycoimmunogen Tn-Thr-PS A1 <i>via</i> hydrazone bond and stability optimization of PS A1 monosaccharide mimics under vaccine development conditions
  作者：F. Hossain、S. Nishat、S. Ghosh、S. Boga、G. T. Hymel、P. R. Andreana

  DOI：10.1080/07328303.2019.1709975

  日期：2020.3.23

  Previously, our group constructed several immunogens utilizing oxime linkage to conjugate a T-cell stimulatory zwitterionic polysaccharide PS A1 and tumor associated carbohydrate antigens (TACAs) in acetate buffer. Here, a semi-synthetic immunogen was synthesized using hydrazone conjugation between PS A1 and a glycopeptide hydrazide (alpha-D-GalNAc-L-Thr-NH-NH2) with an excellent loading in PBS buffer. To get robust immune response, the retention of zwitterionic character of PS A1 under vaccine construction conditions is essential. In this regard, the stability of embedded pyruvate acetal moiety in tetrasaccharide repeating unit of PS A1 can validate the retention of the dual charges. Therefore, rather than utilizing this highly immunogenic PS A1 fully, stability studies were performed with synthetic 1-thiophenyl-4,6-O-pyruvate acetal-D-galactopyranose in varying acetate buffer pHs and time intervals. Furthermore, 1-propyl-D-galactofuranose was synthesized to mimick the D-Galf of PS A1 to examine regioselective hydrazone and oxime formation with alpha-D-GalNAc-L-Thr-NH-NH2 and alpha-D-GalNAc-ONH2 moieties respectively.
• Glycosylation studies on conformationally restricted 3,5-O-(di-tert-butylsilylene)-d-galactofuranosyl trichloroacetimidate donors for 1,2-cis α-d-galactofuranosylation
  作者：Mariano J. Tilve、Carola Gallo-Rodriguez

  DOI：10.1016/j.carres.2011.10.004

  日期：2011.10

  Conformationally restricted 3,5-O-di-tert-butylsilylene-D-galactofuranosyl trichloroacetimidate donors were synthesized from allyl alpha-D-galactofuranoside for the construction of 1,2-cis alpha-D-galactofuranosyl linkages. Glycosylation reactions were performed with several acceptors, including D-galactono-1,4-lactone, D-rhamnopyranosyl, and D-mannopyranosyl derivatives. The influence of the temperature and the reaction solvents was evaluated, as well as the 6-O-substitution pattern of the donor. The higher alpha-selectivities were obtained at -78 degrees C in diethyl ether as solvent. 6-O-Acetyl substitution on constrained donor increased the alpha-selectivity compared to the 6-O-benzyl substitution. Almost no selectivities were observed in the non-participating solvent CH2Cl2. In contrast, ethereal solvents enhanced the alpha-selectivity suggesting a participating effect in the reaction intermediate. (C) 2011 Elsevier Ltd. All rights reserved.