N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-L-serine benzyl ester | 172325-11-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-L-serine benzyl ester
• 英文别名: N-Fmoc-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-L-serine benzyl ester
• CAS: 172325-11-0
• 化学式: C₃₇H₃₈N₄O₁₂
• 分子量: 730.728
• InChiKey: VHSPPZUCLPLXIM-CDBHVMKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.48
• 重原子数：
  53.0
• 可旋转键数：
  14.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  210.75
• 氢给体数：
  1.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-L-serine benzyl ester 在 吡啶 、 palladium on activated charcoal 、 氢气 、 溶剂黄146 作用下， 以 甲醇 、 甲酸 、 水 为溶剂， 反应 2.0h， 生成 N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-acetamido-2-deoxy-α-D-glucopyranosyl)-L-serine
  参考文献：
  名称：

  Enhanced Epimerization of Glycosylated Amino Acids During Solid-Phase Peptide Synthesis

  摘要：

  Glycopeptides are extremely useful for basic research and clinical applications, but access to structurally defined glycopeptides is limited by the difficulties in synthesizing this class of compounds. In this study, we demonstrate that many common peptide coupling conditions used to prepare O-linked glycopeptides result in substantial amounts of epimerization at the a position. In fact, epimerization resulted in up to 80% of the non-natural epimer, indicating that it can be the major product in some reactions. Through a series of mechanistic studies, we demonstrate that the enhanced epimerization relative to nonglycosylated amino acids is due to a combination of factors, including a faster rate of epimerization, an energetic preference for the unnatural epimer over the natural epimer, and a slower overall rate of peptide coupling. In addition, we demonstrate that use of 2,4,6-trimethylpyridine (TMP) as the base in peptide couplings produces glycopeptides with high efficiency and low epimerization. The information and improved reaction conditions will facilitate the preparation of glycopeptides as therapeutic compounds and vaccine antigens.

  DOI：

  10.1021/ja212188r
• 作为产物：
  描述：

  2-azido-2-deoxy-D-glucose 在 吡啶 、 4 A molecular sieve 、 碘 、 六甲基二硅氮烷 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 N-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-L-serine benzyl ester
  参考文献：
  名称：

  Iodine Promoted Glycosylation with Glycosyl Iodides: α‐Glycoside Synthesis

  摘要：

  Glycosidation of fully acetylated glucopyranosyl iodide with methanol under the influence of iodine gave a-glucoside selectively. Use of less reactive acceptors led to the formation of alpha/beta-mixtures. Glycosylations with fully benzoylated glucosyl iodide yielded beta-glucosides only. In contrast, iodine-promoted glycosylation of serine and threonine with 2-azido-2-deoxy-glycosyl iodides, easily obtained in three steps, proceeded smoothly, resulting in only alpha-linked products in high yield in most cases.

  DOI：

  10.1081/car-200067028

文献信息

• Stereoselective synthesis of O-serinyl/threoninyl-2-acetamido-2-deoxy-α- or β-glycosides
  作者：Lajos Szabó、Jan Ramza、Courtney Langdon、Robin Polt

  DOI：10.1016/0008-6215(95)00016-m

  日期：1995.9

  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.