N^α-(9-fluorenylmethoxycarbonyl)-3-O-<3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranosyl>-L-serine | 169061-79-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N^α-(9-fluorenylmethoxycarbonyl)-3-O-<3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranosyl>-L-serine
• 英文别名: N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-deoxy-2-<<(2,2,2-trichloroethoxy)carbonyl>amino>-β-D-glucopyranosyl)-L-serine；N^α-(9-fluorenylmethoxycarbonyl)-3-O-(2-deoxy-2-(2',2',2'-trichloroethoxycarbonylamino)-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-L-serine；N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-deoxy-2-[(2,2,2-trichloroethyloxycarbonyl)amino]-β-D-glucopyranosyl)-L-serine；(2S)-3-[(2R,3R,4R,5S,6R)-4,5-diacetyloxy-6-(acetyloxymethyl)-3-(2,2,2-trichloroethoxycarbonylamino)oxan-2-yl]oxy-2-(9H-fluoren-9-ylmethoxycarbonylamino)propanoic acid
• CAS: 169061-79-4
• 化学式: C₃₃H₃₅Cl₃N₂O₁₄
• 分子量: 790.005
• InChiKey: YXKLKHVKKLWXSC-HEBNFACKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  52
• 可旋转键数：
  18
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  211
• 氢给体数：
  3
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  N^α-(9-fluorenylmethoxycarbonyl)-3-O-<3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranosyl>-L-serine 在 溶剂黄146 、 三乙胺 、 锌 作用下， 以 1,4-二氧六环 为溶剂， 反应 6.0h， 生成 N-(9-fluorenylmethoxycarbonyl)-(2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-L-serine
  参考文献：
  名称：

  Stereoselective synthesis of O-serinyl/threoninyl-2-acetamido-2-deoxy-α- or β-glycosides

  摘要：

  General glycosidation methodology has been developed which can selectively provide 2acetamido-2-deoxy-alpha- or beta-glycosides of beta-hydroxy-alpha-amino acid derivatives [glucopyranoside- (8, 43), galactopyranoside- (9, 13), mannopyranoside- (10), lactoside analogs (11, 38) and 3-O-beta-galactopyranosyl-mannopyranoside (12)] stereoselectively in excellent yield from the highly nucleophilic a-imino esters (Schiff bases) of L-serine and L-threonine. Various glycosides were converted via their amino and acetamido derivatives to Fmoc-protected serinyl- or threoninyl-glycosides (24-28, 37, 41, 46) which are all suitable building blocks for the solid-phase synthesis of O-glycopeptides. Complete H-1- and C-13-NMR data are provided for all compounds.

  DOI：

  10.1016/0008-6215(95)00016-m
• 作为产物：
  描述：

  1,3,4,6-四-O-乙酰基-2-氨基-2-脱氧-Β-D-葡萄糖盐酸盐 在 吡啶 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 N^α-(9-fluorenylmethoxycarbonyl)-3-O-<3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranosyl>-L-serine
  参考文献：
  名称：

  N-Troc保护的糖基供体的糖基化。

  摘要：

  将N-Troc保护的（Troc = 2,2,2-三氯乙氧基羰基）葡萄糖胺和半乳糖胺糖基供体（1-O-乙酰基糖，溴糖和硫代糖苷）与相应的N-Phth保护的衍生物的糖基化为2 -（三甲基甲硅烷基）乙醇，2-溴乙醇，3-巯基丙酸甲酯，N-Fmoc保护的丝氨酸和2-（三甲基甲硅烷基）乙基6-O-苄基-2-脱氧-2-邻苯二甲酰亚胺-β-D-吡喃葡萄糖苷。N-Troc保护的供体比N-Phth保护的供体以更高的收率得到纯的β-糖苷。N-Troc保护基可通过用锌还原来去除，从而允许在同时包含N-Troc和N-Phth基团的寡糖中进行选择性N-脱保护。

  DOI：

  10.1016/0008-6215(95)00318-5

文献信息

• Solid-Phase O-Glycosylation with a Glucosamine Derivative for the Synthesis of a Glycopeptide
  作者：Philip Ryan、Andy Hsien Wei Koh、Anna Elizabeth Lohning、Santosh Rudrawar

  DOI：10.1071/ch17201

  日期：——

  An efficient synthesis of the O-linked glycosylamino acid Fmoc–l-Ser((Ac)3–β-d-GlcNAc)-OH building block is described. The utility of the method was demonstrated with direct solid-phase O-glycosylation of the hydroxyl group on the amino acid (Ser) side chain of a human α-A crystallin-derived peptide (AIPVSREEK) in nearly quantitative glycosylation yield.

  的有效合成的ø -连接glycosylamino酸的Fmoc-升-Ser（（AC）3 -β- d -GlcNAc）-OH积木进行说明。该方法的实用性通过直接固相O-糖基化人类α-A晶状蛋白衍生肽（AIPVSREEK）的氨基酸（Ser）侧链上的羟基而得到证明，几乎可以定量地糖基化。
• Preparation of building blocks for glycopeptide synthesis by glycosylation of Fmoc amino acids having unprotected carboxyl groups
  作者：Lourdes A. Salvador、Mikael Elofsson、Jan Kihlberg

  DOI：10.1016/0040-4020(95)00224-v

  日期：1995.5

  Nα-Fmoc amino acids with an unprotected α-carboxyl group have been glycosylated with carbohydrate 1,2-trans peracetates using Lewis acids as promoters. Aliphatic and phenolic O- and S-glycosides of amino acids, with a 1,2-trans anomeric configuration, were obtained as products in 34–65% yields. The glycosylated building blocks have the protective groups of choice (i.e. O-acetyl and Nα-Fmoc) for direct

  Ñ α -Fmoc氨基酸与未保护的α-羧基已被糖基化的碳水化合物与1,2-反式使用路易斯酸作为促进剂过乙。获得具有1，2-反式异头构型的氨基酸的脂肪族和酚类O-和S-糖苷，收率为34–65％。糖基化的构建块有选择的保护基团（即ø -乙酰基和Ñ α -Fmoc）在糖肽的逐步合成直接使用。起始原料容易获得，并且该方法不需要合成碳水化合物化学方面的丰富经验。
• Synthesis of serine-based glycolipids as potential TLR4 activators
  作者：Li-De Huang、Hong-Jyune Lin、Po-Hsiung Huang、Wei-Chen Hsiao、L. Vijaya Raghava Reddy、Shu-Ling Fu、Chun-Cheng Lin

  DOI：10.1039/c0ob00990c

  日期：——

  orientation of the anomeric glycosidic bond of CCL-34 resulted in a complete loss of activity (β-CCL34). Surprisingly, a change in configuration of the anomeric glycosidic bond in a glucosyl glycolipid is tolerable (CCL-34-S14). Another noteworthy observation is that the activity of a L-fucosyl derived glycolipid (CCL-34-S13) was comparable to that of CCL-34. In sum, this study determines the structural

  通过改变α-GalCer衍生的前导化合物（CCL-34）的脂链长度和糖结构，合理设计了一系列新的不含磷酸基的单糖基糖脂，带有两个脂链），这是一种有效的TLR4激动剂。在稳定表达人TLR4，MD2和CD14（293-hTLR4 / MD2-CD14）的HEK293细胞系中测量了包含60个成员的具有不同脂质链长度的化合物的基于半乳糖基丝氨酸的合成文库的NF-κB活性。结果表明，脂胺和脂肪酸激活TLR4的最佳碳链长度分别为10-11和12。对包含具有各种糖基部分和固定脂链长度的化合物的20元合成基于糖基丝氨酸的脂质文库的评估表明，CCL-34中的半乳糖部分可以被取代葡萄糖而不会丧失活性（CCL-34-S3和CCL-34-S16）。改变CCL-34的异头糖苷键的方向导致活性完全丧失（β-CCL34）。令人惊讶地，糖基糖脂中的异头糖苷键的构型变化是可忍受的（CCL-34-S14）。另一个值得注意的发
• Solid-Phase Synthesis of O-Linked Glycopeptide Analogues of Enkephalin
  作者：Scott A. Mitchell、Matt R. Pratt、Victor J. Hruby、Robin Polt

  DOI：10.1021/jo005712m

  日期：2001.4.1

  The synthesis of 18 N-alpha -FMOC-amino acid glycosides for solid-phase glycopeptide assembly is reported. The glycosides were synthesized either from the corresponding O'Donnell Schiff bases or from N-alpha -FMOC-amino protected serine or threonine and the appropriate glycosyl bromide using Hanessian's modification of the Koenigs-Knorr reaction. Reaction rates of D-glycosyl bromides (e.g., acetobromoglucose) with the L- and D-forms of serine and threonine are distinctly different and can be rationalized in terms of the steric interactions within the two types of diastereomeric transition states for the D/L and D/D reactant pairs. The N-alpha -FMOC-protected glycosides [monosaccharides Xyl, Glc, Gal, Man, GlcNAc, and GalNAc; disaccharides Gal-beta (1-4)-Gle (lactose), Glc-beta-(1-4)-Glc (cellobiose), and Gal-alpha (1-6)-Glc (melibiose)] were incorporated into 22 enkephalin glycopeptide analogues. These peptide opiates bearing the pharmacophore H-Tyr-c[DCys-Gly-PheDCys]- were designed to probe the significance of the glycoside moiety and the carbohydrate-peptide linkage region in blood-brain barrier (BBB) transport, opiate receptor binding, and analgesia.