ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside | 188472-80-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside
• 英文别名: (2S,3R,4S,5R,6R)-2-ethylsulfanyl-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-ol
• CAS: 188472-80-2
• 化学式: C₂₉H₃₄O₅S
• 分子量: 494.652
• InChiKey: BLEKONIUPDUQSX-LLQHYSMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside 在 吡啶 、 4 A molecular sieve 、 sodium methylate 、 三氟甲烷磺酸甲酯 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 8.17h， 生成 5-azidopentyl 2,4,6-tri-O-benzyl-α-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of Fragments of the Glycocalyx Glycan of the ParasiteSchistosoma mansoni

  摘要：

  The chemical synthesis of alpha-L-Fucp-(1 --> 3)-beta-D-GalpNAc-(1 --> 4)-beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2, beta-D-GalpNAc-(1 --> 4)-[alpha-L-Fucp-(1 --> 3)-]beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2, and alpha-L-Fucp-(1 --> 3)-beta-D-GalpNAc-(1 --> 4)- [alpha-L-Fucp-(1 --> 3)-]beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2 is described. These structures represent fucosylated oligosaccharide fragments of the glycocalyx glycan of the cercarial stage of the parasite Schistosoma mansoni, and in protein-conjugated form they are potential diagnostics in the search for antibodies raised against the glycan in the serum of infected humans.

  DOI：

  10.1002/1521-3765(20020104)8:1<151::aid-chem151>3.0.co;2-c
• 作为产物：
  描述：

  ethyl 2,6-di-O-benzyl-3,4-O-isopropylidene-1-thio-β-D-galactopyranoside 在 lithium aluminium tetrahydride 、 三氯化铝 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.43h， 生成 ethyl 2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of Fragments of the Glycocalyx Glycan of the ParasiteSchistosoma mansoni

  摘要：

  The chemical synthesis of alpha-L-Fucp-(1 --> 3)-beta-D-GalpNAc-(1 --> 4)-beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2, beta-D-GalpNAc-(1 --> 4)-[alpha-L-Fucp-(1 --> 3)-]beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2, and alpha-L-Fucp-(1 --> 3)-beta-D-GalpNAc-(1 --> 4)- [alpha-L-Fucp-(1 --> 3)-]beta-D-GlcpNAc-(1 --> 3)-alpha-D-GalpO(CH2)(5)NH2 is described. These structures represent fucosylated oligosaccharide fragments of the glycocalyx glycan of the cercarial stage of the parasite Schistosoma mansoni, and in protein-conjugated form they are potential diagnostics in the search for antibodies raised against the glycan in the serum of infected humans.

  DOI：

  10.1002/1521-3765(20020104)8:1<151::aid-chem151>3.0.co;2-c

文献信息

• Synthesis of Hexp-(1 → 4)-β-d-GlcpNac-(1 → 2)-α-d-Manp-(1 → O)(CH2)7CH3 probes for exploration of the substrate specificity of glycosyltransferases: Part II, Hex = 3-O-methyl-β-d-Gal, 3-deoxy-β-d-Gal, 3-deoxy-3-fluoro-β-d-Gal, 3-amino-3-deoxy-β-d-Gal, β-d-Gul, α-l-Alt, or β-l-Gal11Dedicated to Professor Dr. Hans Paulsen on the occasion of his 75th birthday.
  作者：Johannes A.L.M van Dorst、Cornelis J van Heusden、Jaana M Tikkanen、Johannis P Kamerling、Johannes F.G Vliegenthart

  DOI：10.1016/s0008-6215(96)00266-2

  日期：1997.1

  -Man p -(1 → O)(CH 2 ) 7 CH 3 , 3-deoxy-3-fluoro-β- d -Gal p -(1 → 4)-β- d -Glc p NAc-(1 → 2)-α- d -Man p -(1 → O)(CH 2 ) 7 CH 3 , 3-amino-3-deoxy-β- d -Gal p -(1 → 4)-β- d -Glc p NAc-(1 → 2)-α- d -Man p -(1 → O)(CH 2 ) 7 CH 3 , β- d -Gul p -(1 → 4)-β- d -Glc p NAc-(1 → 2)-α- d -Man p -(1 → O)(CH 2 ) 7 CH 3 , β- l -Gal p -(1 → 4)-β- d -Glc p NAc-(1 → 2)-α- d -Man p -(1 → O)(CH 2 ) 7 CH 3 , and α- l -Alt

  摘要三糖β-d -Gal p-（1→4）-β-d -Glc p NAc-（1→2）-α-d -Man p-（1→O）（CH 2）7的七个类似物已经合成了CH 3作为参与N-乙酰基乳糖胺型N-聚糖的链终止的糖基转移酶的潜在底物。这些化合物包括：3-O-甲基-β-d -Gal p-（1→4）-β-d -Glc p NAc-（1→2）-α-d -Man p-（1→O）（ CH 2）7 CH 3，3-脱氧-β-d-Gal p-（1→4）-β-d-Glc p NAc-（1→2）-α-d -Man p-（1→O） （CH 2）7 CH 3，3-脱氧-3-氟-β-d-Gal p-（1→4）-β-d-Glc p NAc-（1→2）-α-d-Man p- （1→O）（CH 2）7 CH 3，3-氨基-3-脱氧-β-d-Gal p-（1→4）-β-d -Glc p NAc-（1→2）-α- d -Man p-（1→O）（CH
• The presence of water improves reductive openings of benzylidene acetals with trimethylaminoborane and aluminium chloride
  作者：Andrei A. Sherman、Yuri V. Mironov、Olga N. Yudina、Nikolay E. Nifantiev

  DOI：10.1016/s0008-6215(03)00015-6

  日期：2003.4

  efficient for the reductive openings of the cyclic benzylidene acetals with Me(3)N x BH(3) in tetrahydrofurane than the AlCl(3) alone. Under proposed conditions, the dioxane-type 4,6-O-bezylidene acetals of hexopyranosides give regioselectively the corresponding 4-hydroxy,6-O-benzyl derivatives in excellent yields. Reductive openings of the dioxolane-type 3,4-O-benzylidene acetals of galactopyranoside are

  由无水AlCl（3）和H（2）O以3：1比例原位形成的酸性试剂比四氢呋喃中Me（3）N x BH（3）还原环亚苄基乙缩醛的效率高得多单独的AlCl（3）。在提出的条件下，己吡喃糖苷的二恶烷型4，6-O-亚苄基乙缩醛以优异的产率选择性地给出相应的4-羟基，6-O-苄基衍生物。半乳糖吡喃糖苷的二氧戊环型3,4-O-亚苄基乙缩醛的还原开口也非常有效且具有区域选择性，可生成3-O-苄基衍生物（来自3,4-O-外亚苄基乙缩醛）或4-O-苄基衍生物（来自3,4-O-内-亚苄基缩醛）取决于缩醛碳原子的构型。
• ——
  作者：P. E. Cheshev、E. A. Khatuntseva、A. G. Gerbst、Yu. E. Tsvetkov、A. S. Shashkov、N. E. Nifantiev

  DOI：10.1023/a:1024905419008

  日期：——

  selectively protected derivatives of tetrasaccharide GalNAc(beta 1-->3)Gal(alpha 1-->4)Gal(beta 1-->4)Glc beta-OCH2CH2N3 and pentasaccharide Gal(beta 1-->3)GalNAc(beta 1-->3)Gal(alpha 1-->4)Gal(beta 1-->4)Glc beta-OCH2CH2N3 in 88 and 73% yields, respectively. Removal of O-protecting groups, substitution of acetyl group for N-trichloroacetyl group, and reduction of the aglycone azide group resulted in the

  6-三-O-乙酰基-2-脱氧-1-硫代-2-三氯乙酰氨基-β-D-吡喃半乳糖苷和4-三氯乙酰胺基苯基4,6-二-O-乙酰基-2-脱氧-3-O-（2，在N-碘代琥珀酰亚胺和三氟甲磺酸存在下，二氯甲烷中的3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基）-1-硫-2-三氯乙酰胺基-β-D-吡喃半乳糖苷导致相应的选择性保护四糖GalNAc（β1-> 3）Gal（α1-> 4）Gal（β1-> 4）Glcβ-OCH2CH2N3的衍生物和五糖Gal（β1-> 3）GalNAc（β1- -> 3）Gal（alpha 1-> 4）Gal（beta 1-> 4）Glc beta-OCH2CH2N3，产率分别为88％和73％。除去O-保护基，将乙酰基替换为N-三氯乙酰基，以及将糖苷配基叠氮基还原，得到目标2-氨基乙基球蛋白三-，-四-和-五糖，
• Synthesis of β‐Glucosides with 3‐ <i>O</i> ‐Picoloyl‐Protected Glycosyl Donors in the Presence of Excess Triflic Acid: Defining the Scope
  作者：Michael P. Mannino、Alexei V. Demchenko

  DOI：10.1002/chem.201905278

  日期：2020.3.2

  Excellent β-stereoselectivity for the glycosylation with glucosyl donors equipped with the 3-O-picoloyl (Pico) group, without the use of participating group, was achieved in the presence of NIS/excess TfOH promoter system. A complete investigation of the scope of this reaction was performed, revealing all important attributes of successful glycosylation. While altering the halogen source was tolerated

  在存在NIS /过量TfOH启动子系统的情况下，在不使用参与基团的情况下，对于配备有3-O-picoloyl（Pico）基团的葡萄糖基供体的糖基化具有出色的β-立体选择性。对该反应范围进行了全面研究，揭示了成功糖基化的所有重要属性。在容忍改变卤素源的同时，三氟甲磺酸根阴离子的取代导致立体选择性的完全丧失。经确定，Pico基团的质子化在该反应中至关重要。还发现质子化吡啶环的稳定性或程度是获得高立体选择性的另一个重要关键因素。发现受体的亲核性与所获得的立体选择性成正比，暗示了类似于SN 2的机制。
• Synthesis of oligosaccharides corresponding to Streptococcus pneumoniae type 9 capsular polysaccharide structures
  作者：Mia Alpe、Stefan Oscarson

  DOI：10.1016/s0008-6215(02)00263-x

  日期：2002.10

  alpha-D-Glcp-(1-->3)-beta-D-ManpNAc-(1-->4)-beta-D-Glcp, corresponding to structures from Streptococcus pneumoniae capsular polysaccharides type 9A, L, V and type 9N, respectively, have been synthesised as 2-aminoethyl glycosides and as protected TMSE glycosides. Ethyl thioglycosides were used as glycosyl donors and NIS/TfOH (in CH(2)Cl(2) for beta-linkages) and DMTST (in Et(2)O for alpha-linkages) as promoters

  两种三糖，α-D-Galp-（1-> 3）-beta-D-ManpNAc-（1-> 4）-beta-D-Glcp和alpha-D-Glcp-（1-> 3） -β-D-ManpNAc-（1-> 4）-β-D-Glcp分别对应于肺炎链球菌荚膜多糖9A，L，V和9N型多糖的结构，已被合成为2-氨基乙基糖苷和作为受保护的TMSE糖苷。乙基硫代糖苷用作糖基供体，而NIS / TfOH（对于β键，则在CH（2）Cl（2）中）和DMTST（对于α键，则在Et（2）O中）用作糖基化促进剂。通过叠氮化置换具有β-D-葡萄糖构型的2-O-三氟甲磺酸酯，可以在二糖水平上引入β-ManNAc基序。保护基图案允许连续合成更大的结构。