methyl 6-O-(3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside | 131326-67-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-(3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: [(2S,4aR,6R,7R,8R,8aR)-7-azido-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] acetate
• CAS: 131326-67-5
• 化学式: C₄₃H₄₇N₃O₁₁
• 分子量: 781.86
• InChiKey: AQBXQTRFTXOHBQ-ANGZOLEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  57
• 可旋转键数：
  17
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  methyl 6-O-(3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 methyl 6-O-(2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  一类新颖的糖基供体：2-叠氮基-2-脱氧-D-吡喃半乳糖基衍生物的端基S-黄原酸酯

  摘要：

  通过相应半乳糖（1,5-脱水-2-脱氧-D- lyxo）的两步叠氮蒽并化反应，可以轻松制备各种取代的O-乙基S-（2-叠氮基-2-脱氧-D-吡喃半乳糖基）二硫代碳酸酯。（-hex-1-enitols）。它们是有效的糖基供体，用于立体选择性地合成具有生物学重要性的含半乳糖胺的寡糖的保护前体。

  DOI：

  10.1016/s0040-4020(01)87127-1
• 作为产物：
  描述：

  3-O-acetyl-1,5-anhydro-4,6-O-benzylidene-2-deoxy-D-lyxo-hex-1-enitol 在 sodium azide 、 ammonium cerium(IV) nitrate 、 4 A molecular sieve 、 DMTST 作用下， 以 乙腈 为溶剂， 反应 10.0h， 生成 methyl 6-O-(3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  一类新颖的糖基供体：2-叠氮基-2-脱氧-D-吡喃半乳糖基衍生物的端基S-黄原酸酯

  摘要：

  通过相应半乳糖（1,5-脱水-2-脱氧-D- lyxo）的两步叠氮蒽并化反应，可以轻松制备各种取代的O-乙基S-（2-叠氮基-2-脱氧-D-吡喃半乳糖基）二硫代碳酸酯。（-hex-1-enitols）。它们是有效的糖基供体，用于立体选择性地合成具有生物学重要性的含半乳糖胺的寡糖的保护前体。

  DOI：

  10.1016/s0040-4020(01)87127-1

文献信息

• A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-d-glycosyl diphenyl phosphates as glycosyl donors
  作者：Toshifumi Tsuda、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/j.tet.2004.08.076

  日期：2004.11

  The scope of TMSOTf-promoted glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates is investigated. The 3,4,6-tri-O-benzyl-protected glucosyl and galactosyl donors and the 4,6-O-benzylidene-protected galactosyl donor each react with a range of acceptor alcohols in the presence of a stoichiometric amount of TMSOTf in propionitrile at -78 degreesC to afford 1,2-trans-beta-linked disaccharides in high yields with alpha:beta ratios ranging from 9:91 to 1: > 99, regardless of the anomeric composition of the donor used. The use of propionitrile as a solvent at -78 degreesC has proven to be among the best choice for the highest levels of beta-selectivity reported to date for this type of glycosidation. A plausible reaction mechanism, which features a large equilibrium preference for alpha-glycosyl-nitrilium ions over beta-nitrilium ions, is proposed based on byproducts formed through their intermediacy and accounts for the observed excellent beta-selectivities. (C) 2004 Elsevier Ltd. All rights reserved.
• A stereocontrolled construction of 2-azido-2-deoxy-1,2-cis-α-galactosidic linkages utilizing 2-azido-4,6-O-benzylidene-2-deoxygalactopyranosyl diphenyl phosphates: stereoselective synthesis of mucin core 5 and core 7 structures
  作者：Kosuke Kakita、Toshifumi Tsuda、Noritoshi Suzuki、Seiichi Nakamura、Hisanori Nambu、Shunichi Hashimoto

  DOI：10.1016/j.tet.2012.04.059

  日期：2012.6

  TMSOTf-promoted glycosidation of 2-azido-4,6-O-benzylidene-2-deoxygalactosyl diphenyl phosphates with fluorenylmethoxycarbonyl (Fmoc)-protected serine and threonine derivatives in THF/Et2O (1:1) gave glycosyl amino acids in high yields and with excellent levels of alpha-selectivity (alpha/beta=94:6-95:5). The synthetic utility of the present glycosidation method was demonstrated by a stereoselective synthesis of mucin-type glycopeptide core 5 and core 7 building blocks, which are suitable for Fmoc-based solid-phase synthesis of O-glycopeptides. (C) 2012 Elsevier Ltd. All rights reserved.