ethyl 2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside | 186665-14-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside
• 英文别名: ethyl 2-deoxy-1-thio-2-(2,2,2-trichloroethoxy)carbonylamino-β-D-glucopyranoside；TrocNH(-2d)Glc(b)-SEt；2,2,2-trichloroethyl N-[(2S,3R,4R,5S,6R)-2-ethylsulfanyl-4,5-dihydroxy-6-(hydroxymethyl)oxan-3-yl]carbamate
• CAS: 186665-14-5
• 化学式: C₁₁H₁₈Cl₃NO₆S
• 分子量: 398.692
• InChiKey: YWWLDNJYMOQCMU-OKNNCHMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  134
• 氢给体数：
  4
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 甲磺酰溴 、 3 Angstroems MS 、 氢气 、 silver trifluoromethanesulfonate 、 sodium cyanoborohydride 、 对甲苯磺酸 、 乙二胺 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 31.08h， 生成
  参考文献：
  名称：

  Synthesis of Lactam and Acetamido Analogues of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide

  摘要：

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (15) with the donors ethyl 3,4-di-O-acetyl-6-O-benzyl-2-deoxy-2-[[(2,2,2-trichloroethoxy)carbonyl]amino]-1-beta-D-galactopyranoside (14), 4-methylphenyl 2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-1-thio-beta-D-galactopyranoside (30), and 4-methylphenyl 2-O-acetyl-4-azido-6-O-benzyl-4-deoxy-3-O-(methoxyethanoyl)-1-thio-beta-D-galactopyranoside (44) gave the lactose-diamine derivatives 16, 33, and 45, respectively. Fucosylation of the NHAc derivatives of 16 and 33 (17 and 34) with the donor 18 gave, after deprotection and N-acetylation, the 2-NHAc-Le(x) and 4-NKAc-Le(x) trisaccharides 3 and 5, respectively. Removal of the Troc group from the tetrasaccharide intermediate 23, followed by N-acetylation (-->24), gave the NHAc-SLe(x) tetrasaccharide 2. Regioselective sialylation of the partially protected trisaccharide diols 21 and 37 with the sialyl donors 22 and 38 gave, after deprotection and lactamization, the SLe(x)-1'''-->2-lactam 1 and the SLe(x)-1'''-->4'-lactam 4, respectively. The stannylidene acetal of the trisaccharide diol 21 was regioselectively 3-O-alkylated with tert-butyl bromoacetate; reductive removal of the Tree protecting group and addition of methanolic MeONa caused formation of a lactam ring. Compound 40 was thus obtained over four steps in an overall yield of 52%. Deprotection of 40 furnished the Le(x)-3,2-lactam 6 in 74% yield. Fucosylation of the lactose-diamine derivative 46 with donor 18 gave the N-3-Le(x) trisaccharide derivative 47. The azido function of 47 was reduced with H2S, which caused spontaneous closure of a lactam ring. Removal of the protecting groups then gave the Le(x)-3,4-lactam 7. The total yields of 1, 2, 3, 4, 5, and 7 from the monosaccharide starting materials 14, 15, 18, 22, 30, 38, and 44 were 10%, 10%, 22%, 14%, 62%, and 28%, respectively.

  DOI：

  10.1021/jo981204p
• 作为产物：
  描述：

  ethyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside 在 guanidinium nitrate 、 胍 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 以94%的产率得到ethyl 2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  胍/硝酸胍; 一种温和的选择性O-脱乙酰基试剂，可保持N -Troc基团完好无损

  摘要：

  用甲醇胍/硝酸胍的甲醇溶液处理O-乙酰基保护的糖可除去乙酰基（分离产率为91–99％），而不会影响其他保护基。除去O-苯甲酰基需要更长的反应时间。在这些弱碱性反应条件下，2,2,2-三氯乙氧羰基氨基（N -Troc）基团的稳定性特别有价值。

  DOI：

  10.1016/s0040-4039(97)00105-6

文献信息

• Regioselective Glycosylation Strategies for the Synthesis of Group Ia and Ib <i>Streptococcus</i> Related Glycans Enable Elucidating Unique Conformations of the Capsular Polysaccharides
  作者：Linda Del Bino、Ilaria Calloni、Davide Oldrini、Maria Michelina Raso、Rossella Cuffaro、Ana Ardá、Jeroen D. C. Codée、Jesús Jiménez‐Barbero、Roberto Adamo

  DOI：10.1002/chem.201903527

  日期：2019.12.18

  polysaccharides share high structural similarity. Both are composed of the same monosaccharide residues and differ only in the connection of the Neu5Acα2-3Gal side chain to the GlcNAc unit, which is a β1-4 linkage in serotype Ia and a β1-3 linkage in serotype Ib. The development of efficient regioselective routes for GlcNAcβ1-3[Glcβ1-4]Gal synthons is described, which give access to different group B Streptococcus

  B 组链球菌血清型 Ia 和 Ib 荚膜多糖是疫苗开发的关键目标。尽管它们具有免疫特异性，但这些多糖具有高度的结构相似性。两者均由相同的单糖残基组成，不同之处仅在于 Neu5Acα2-3Gal 侧链与 GlcNAc 单元的连接，在血清型 Ia 中为 β1-4 连接，在血清型 Ib 中为 β1-3 连接。描述了 GlcNAcβ1-3[Glcβ1-4]Gal 合成子的有效区域选择性途径的开发，该途径提供了不同 B 族链球菌 (GBS) Ia 和 Ib 重复单元移码的途径。这些聚糖用于探测两种多糖的构象和分子动力学，突出显示突出的 Neu5Acα2-3Gal 部分在多糖主链上的不同呈现方式，以及 Ib 聚合物相对于 Ia 具有更高的灵活性，这可能会影响表位暴露。
• Syntheses of Modified Carbohydrates with Glycosidases: Stereo- and Regiospecific Syntheses of Lactosamine Derivatives and Related Compounds¹
  作者：Kurt G.I. Nilsson、Hefeng Pan、Ulla Larsson-Lorek

  DOI：10.1080/07328309708007328

  日期：1997.5

  Abstract Different lactosamine derivatives, modified in the 2-N- and anomeric positions and suitable as intermediates for synthesis of Lewis-x and related compounds, were prepared with high specificity on a multigram scale directly from lactose, employing different D-glucosamine derivatives as acceptors and the abundant β-D-galactosidase from Bullera singularis as catalyst. Thus, methyl O-β-D-gala

  摘要以不同的D-葡萄糖胺衍生物为接受剂，直接从乳糖以高克数级制备了在2-N-和端基异构体位置修饰，适合作为Lewis-x及相关化合物合成中间体的不同乳糖胺衍生物。并以奇异布拉氏菌中丰富的β-D-半乳糖苷酶为催化剂。因此，甲基O-β-D-吡喃半乳糖基-（1→4）-2-叠氮基-2-脱氧-β-D-吡喃葡萄糖苷，乙基O-β-D-吡喃半乳糖基-（1→4）-2-脱氧- 2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃葡萄糖苷和乙基O-β-D-吡喃半乳糖基-（1→4）-2-脱氧-2-（2,2,2-三氯乙氧基羰基氨基）-1-硫基-β -D-吡喃葡萄糖苷以基于添加的受体计算的20-40％的产率形成。不经色谱法（萃取/结晶步骤）分离出结晶形式的2-邻苯二甲酰亚胺基衍生物。三糖衍生物乙基O-β-D-吡喃半乳糖-（1→4）-O-β-D-吡喃半乳糖-（1→4）-2-脱氧-2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃葡萄糖苷也孤立。对应
• Comparison of the Armed/Disarmed Building Blocks of the <scp>d</scp>-Gluco and <scp>d</scp>-Glucosamino Series in the Context of Chemoselective Oligosaccharide Synthesis
  作者：Teerada Kamkhachorn、Archana R. Parameswar、Alexei V. Demchenko

  DOI：10.1021/ol101089u

  日期：2010.7.2

  A very elegant Fraser-Reid armed-disarmed approach recently expanded to the building blocks of the superarmed and superdisarmed series shows very high utility in chemoselective oligosaccharide synthesis. Although a number of studies dedicated to the chemoselective activation of 2-amino-2-deoxysugars have emerged, little remains known about how the reactivity of the armed/disarmed building blocks of the neutral sugars directly compares to that of their 2-aminosugar counterparts. A preliminary study of this comparative reactivity is presented.
• Glycosidase-catalysed synthesis of di- and trisaccharide derivatives related to antigens involved in the hyperacure rejection of xenotransplants
  作者：Kurt G.I. Nilsson

  DOI：10.1016/s0040-4039(96)02235-6

  日期：1997.1

  A convenient enzymatic procedure, suitable for large scale preparation of the beta-thioethyl 2-N-Teoc-derivative of Ga1 alpha 1-3Gal beta 1-4GlcNAc, GalS1-4GlcNAc, is described (Teoc = 2,2,2-trichloroethoxycarbonyl). beta-D-Galactosidase from Bullera singularis was used for the specific synthesis of Gal beta 1-4GlcNTeoc beta-SEt from lactose and D-GlcNTeoc beta-SEt. alpha-D-Galactosidase from coffee beans was used for the stereo- specific and highly regioselective preparation of Gal alpha 1-3Gal beta 1-4GlcNTeoc beta-SEt, employing D-Gal alpha-OPhNO(2)-p as glycosyl donor and Gal beta 1-4GlcNTeoc beta-SEt as acceptor. Copyright (C) 1996 Elsevier Science Ltd
• GALACTOPYRANOSIDES AND THEIR USE
  申请人：Procur AB

  公开号：EP0873414A1

  公开（公告）日：1998-10-28