methyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside

• 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: methyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: Methyl 2,3-di-O-benzoyl-4,6-O-benzylidene-a-D-glucopyranoside；[(2R,4aR,6S,7R,8S,8aR)-7-benzoyloxy-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate
• 化学式: C₂₈H₂₆O₈
• 分子量: 490.51
• InChiKey: CGMUHSNJRXPSSA-LUKJHSJDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 在 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 methyl 2,3,6-tri-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  The Synthesis of Active-Site Directed Inhibitors of Some β-Glucan Hydrolases

  摘要：

  制备出了 D-葡萄糖、纤维生物糖和片状生物糖的 2,3-环氧丙基、3,4-环氧丁基和 4,5-环氧戊基 β-糖苷。此外，还合成了纤维三糖、片状三糖和另外两种三糖的 4,5-环氧戊基 β-糖苷。此外，还制备了 3,4-环氧丁基 β-纤维二糖苷，并在纤维二糖残基中添加了 14C 标记。

  DOI：

  10.1071/ch9900665
• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 在 2,4,6-三甲基吡啶 、 copper(II) trifluoroacetate 、 gadolinium(III) trifluoroacetate 作用下， 以 乙腈 为溶剂， 反应 12.0h， 生成 methyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Regioselective Benzoylation of 4,6-O-Benzylidene Acetals of Glycopyranosides in the Presence of Transition Metals

  摘要：

  Benzoylation of 4,6-O-benzylidene acetals of glycopyranosides by benzoic anhydride in acetonitrile in the presence of Cu(CF3COO)(2) as a promoter gave 2-benzoates for alpha-D-glucopyranosides and alpha-D-mannopyranosides and 3-benzoates for beta-D-galactopyranosides in good yields with high regioselectivity. Benzoylation of 4,6-O-benzylidene acetals of glycopyranosides of D-galactose and D-mannose by benzoyl chloride in the presence of MoO2(acac)(2) as a catalyst in all studied cases led to regioselective 3-O-substitution.

  DOI：

  10.1080/07328303.2014.996291

文献信息

• Stannous chloride as a low toxicity and extremely cheap catalyst for regio-/site-selective acylation with unusually broad substrate scope
  作者：Jian Lv、Jian-Cheng Yu、Guang-Jing Feng、Tao Luo、Hai Dong

  DOI：10.1039/d0gc02739a

  日期：——

  containing cis-vicinal diol, the substrate scope also includes glycosides without cis-vicinal diol. For such a substrate scope, usually, only methods using stoichiometric amounts of organotin reagents can lead to the same protection pattern with high selectivities and highly isolated yields (84–97% in most cases). Therefore, SnCl2, as a low toxicity and extremely cheap reagent, should be the best catalyst

  这项工作报告了氯化亚锡（SnCl 2）催化的区域/位点选择性酰化反应，其底物范围异常广泛。除了含有顺式-邻位二醇的1,2-和1,3-二醇和糖苷外，底物范围还包括不含顺式-邻位二醇的糖苷。对于这种底物范围，通常，只有使用化学计量的有机锡试剂的方法才能以高选择性和高分离产率（大多数情况下为84–97％）产生相同的保护模式。因此，与以前报道的任何试剂相比，SnCl 2作为一种低毒且极其便宜的试剂，应该是区域/位点选择性酰化反应的最佳催化剂。
• 2,4,6-Trichloro-1,3,5-triazine (TCT) mediated one-pot sequential functionalisation of glycosides for the generation of orthogonally protected monosaccharide building blocks
  作者：Madhubabu Tatina、Syed Khalid Yousuf、Debaraj Mukherjee

  DOI：10.1039/c2ob25452b

  日期：——

  Orthogonally protected monosaccharide building blocks have been prepared using TCT in a one-pot multicomponent transformation. The process involves successive steps of arylidene acetalation, esterification and regioselective reductive acetal cleavage. High regioselectivity, scope for using a broad range of substrates, functional group tolerance, mild reaction conditions, easy handling process and wide application range are a few advantages of the current process.

  利用TCT（三氯乙酰亚胺基）在一锅多组分转化中制备了正交保护的单糖构建块。该过程包括连续的芳亚基缩醛化、酯化和区域选择性还原开环反应步骤。高区域选择性、广泛的底物适用范围、官能团的耐受性、温和的反应条件、易于操作以及广泛的应用范围是该当前过程的一些优点。
• Efficient Formation and Cleavage of Benzylidene Acetals by Sodium ­Hydrogen Sulfate Supported on Silica Gel
  作者：Xin-Shan Ye、Youhong Niu、Ning Wang、Xiaoping Cao

  DOI：10.1055/s-2007-984903

  日期：——

  NaHSO 4 ·SiO 2 was used as an efficient heterogeneous catalyst for both the formation and the cleavage of benzylidene -acetals. This catalyst is compatible with many functional or protective groups. Under different solvent systems, either the formation or the cleavage of benzylidene acetals was carried out smoothly in -excellent yields and with good chemoselectivity.

  NaHSO 4 ·SiO 2 被用作一种有效的多相催化剂，用于苯亚甲基-缩醛的形成和裂解。该催化剂与许多官能团或保护基团相容。在不同的溶剂体系下，亚苄基乙缩醛的形成或裂解均以优异的收率和良好的化学选择性顺利进行。
• Synthesis of the first pseudosugar-C-disaccharide. A potential antigen for eliciting glycoside-bond forming antibodies with catalytic groups
  作者：Christel Barbaud、Mikael Bols、Inge Lundt、Michael R. Sierks

  DOI：10.1016/0040-4020(95)00505-3

  日期：1995.8

  A number of synthetic routes to the first pseudo-C-disaccharide ever prepared has been studied. The compound, methyl 7-((1S,3R,4R,5S,6S)-1-amino-3-hydroxymethyl-4,5,6trihydroxycyclohexyl) -6,7-dideoxy-α-D-gluco-heptopyranoside (1), is structurally related to cellobiose, but includes a crucial amino-functionality at the pseudoanomeric centre. It was prepared by 1,2-addition of the anion of methyl 6

  已经研究了许多制备第一个假C-二糖的合成途径。化合物7-（（（1S，3R，4R，5S，6S）-1-氨基-3-羟甲基-4,5,6三羟基环己基）-6,7-二脱氧-α-D-葡萄糖-庚基吡喃糖苷（1）与纤维二糖在结构上相关，但在假异构中心具有关键的氨基功能。它是通过将1,6,7-二脱氧-2,3,4-三-O-苄基-α-D-葡萄糖-庚基-6吡喃吡喃果糖苷的阴离子1,2-加成到（4R，5S，6R）-3-苄氧基甲基-4,5,6-三苄氧基-2-环己烯酮，然后将叔醇立体选择性转化为叠氮化物，最后还原。
• Cleavage of 4,6-O-Benzylidene Acetal Using Sodium Hydrogen Sulfate Monohydrate
  作者：Masahiko Hayashi、Kyosuke Michigami、Manami Terauchi

  DOI：10.1055/s-0033-1338469

  日期：——

  using sodium hydrogen sulfate monohydrate under mild conditions. The use of protecting groups is an important protocol in carbohydrate synthesis. Among protecting groups, benzylidene acetals­ are generally more stable than other acetals; therefore, strong conditions are often required for deprotection. We report the deprotection of 4,6-O-benzylidene derivatives using sodium hydrogen sulfate monohydrate

  摘要 保护基的使用是碳水化合物合成中的重要方案。在保护基中，亚苄基乙缩醛通常比其他乙缩醛更稳定。因此，脱保护通常需要严格的条件。我们报道了在温和的条件下使用一水合硫酸氢钠对4,6- O-亚苄基衍生物的脱保护。 保护基的使用是碳水化合物合成中的重要方案。在保护基中，亚苄基乙缩醛通常比其他乙缩醛更稳定。因此，脱保护通常需要严格的条件。我们报道了在温和的条件下使用一水合硫酸氢钠对4,6- O-亚苄基衍生物的脱保护。