2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl trichloroacetimidate | 1000813-74-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl trichloroacetimidate
• 英文别名: 4,6-O-benzylidene-2,3-di-O-benzyl-D-mannopyranosyl trichloroacetimidate；[(2R,4aR,7S,8S,8aR)-2-phenyl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl] 2,2,2-trichloroethanimidate
• CAS: 1000813-74-0
• 化学式: C₂₉H₂₈Cl₃NO₆
• 分子量: 592.903
• InChiKey: RUWQCKVLXFTLBX-DREDECLHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  39
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  79.2
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  双丙酮葡萄糖 、 2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl trichloroacetimidate 在 3 A molecular sieve 、 lithium perchlorate 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以44%的产率得到1,2:5,6-di-O-isopropylidene-3-O-(2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl)-α-D-glucofuranoside
  参考文献：
  名称：

  4,6‐O‐Benzylidene Directed β‐Mannosylation Without Intermediate Triflate Formation? Comparison of Trichloroacetimidate and DISAL Donors in Microwave‐Promoted Glycosylations under Neutral Conditions

  摘要：

  4,6-Benzylidene-protected marmosyl donors have emerged as efficient tools for the formation of 1,2-cis beta-mannosides, which otherwise are difficult to access. Previously studied sulfoxide and trichloroacetimidate mannosyl donors were activated with strong Lewis acids at low temperature and the glycosylations are believed to proceed through intermediate formation of an a-triflate. This paper describes the synthesis of new benzylidene-protected glucosyl and marmosyl methyl 3,5-dinitrosalicylate (DISAL) donors, their application in O-glycosylations, and comparison with a mannosyl trichloroacetimidate donor. In contrast to previous reports on torsionally "disarmed" donors, these glycosylations were performed in the absence of strong Lewis acids, but in the presence of lithium perchlorate or triflate, using either conventional heating to 40 to 60 degrees C or precise microwave heating to 100 to 150 degrees C. This approach aimed at addressing the question of whether marmosyl triflate intermediates are essential for high P-selectivity in 4,6-O-benzylidene directed mannosylations. We find, again, that precise microwave heating promoted glycosylations under very mild conditions.

  DOI：

  10.1080/07328300701634762
• 作为产物：
  描述：

  2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranose 、 三氯乙腈 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranosyl trichloroacetimidate
  参考文献：
  名称：

  4,6‐O‐Benzylidene Directed β‐Mannosylation Without Intermediate Triflate Formation? Comparison of Trichloroacetimidate and DISAL Donors in Microwave‐Promoted Glycosylations under Neutral Conditions

  摘要：

  4,6-Benzylidene-protected marmosyl donors have emerged as efficient tools for the formation of 1,2-cis beta-mannosides, which otherwise are difficult to access. Previously studied sulfoxide and trichloroacetimidate mannosyl donors were activated with strong Lewis acids at low temperature and the glycosylations are believed to proceed through intermediate formation of an a-triflate. This paper describes the synthesis of new benzylidene-protected glucosyl and marmosyl methyl 3,5-dinitrosalicylate (DISAL) donors, their application in O-glycosylations, and comparison with a mannosyl trichloroacetimidate donor. In contrast to previous reports on torsionally "disarmed" donors, these glycosylations were performed in the absence of strong Lewis acids, but in the presence of lithium perchlorate or triflate, using either conventional heating to 40 to 60 degrees C or precise microwave heating to 100 to 150 degrees C. This approach aimed at addressing the question of whether marmosyl triflate intermediates are essential for high P-selectivity in 4,6-O-benzylidene directed mannosylations. We find, again, that precise microwave heating promoted glycosylations under very mild conditions.

  DOI：

  10.1080/07328300701634762

文献信息

• Synthesis of a Tetrasaccharide Related to the Repeating Unit of the Antigen from<i>Shigella dysenteriae</i>Type 9 in the Form of Its 2‐(Trimethylsilyl)ethyl Glycoside
  作者：Samarpita Roy、Sujit Kumar Sarkar、Nirmolendu Roy

  DOI：10.1081/scc-120028645

  日期：2004.12.31

  Abstract Starting from D‐mannose, D‐galactose and D‐glucosamine hydrochloride, two disaccharide blocks were synthesized. Schmidt's inverse addition technique for trichloroacetimidate was utilized for the construction of a disaccharide with a β‐mannosidic linkage in good yield. The two disaccharides in the appropriate form were then allowed to react in the presence of N‐iodosuccinimide (NIS) and tr

  摘要 以 D-甘露糖、D-半乳糖和 D-氨基葡萄糖盐酸盐为原料，合成了两种二糖嵌段。Schmidt 的三氯乙酰亚胺反加成技术用于构建具有 β-甘露糖苷键的双糖，收率良好。然后让两种适当形式的二糖在 N-碘代琥珀酰亚胺 (NIS) 和三氟甲磺酸 (TfOH) 存在下反应，得到四糖衍生物，从中去除保护基团得到所需的四糖形式的 2- (三甲基甲硅烷基)乙基糖苷。
• Highly β-Selective Mannosylation towards Manβ1-4GlcNAc Synthesis: TMSB(C₆F₅)₄as a Lewis Acid/Cation Trap Catalyst
  作者：Koichi Fukase、Shin-ichi Tanaka、Mamoru Takashina、Hiroomi Tokimoto、Yukari Fujimoto、Katsunori Tanaka

  DOI：10.1055/s-2005-872678

  日期：——

  Highly β-selective mannosylation of 4,6-O-benzylidene-mannopyranosyl-N-phenyltrifluoroacetimidate (α/β, 5:95, 93% yield) has been realized by utilizing a dual Lewis acid/cation trap catalyst, TMSB(C6F5)4. The obtained Manβ1-4GlcNTroc unit can be readily converted to a variety of N-linked oligosaccharides.

  4,6-O-亚苄基-甘露糖基-N-苯基三氟乙酰亚胺酯的高度 β 选择性甘露糖基化（α/β，5:95，93% 收率）已通过使用双路易斯酸/阳离子捕获催化剂 TMSB(C6F5) 实现)4.获得的Manβ1-4GlcNTroc 单位可以很容易地转化为各种N 连接寡糖。