3,4,6-tri-O-benzyl-α-D-glucopyranosyl chloride | 74372-91-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,4,6-tri-O-benzyl-α-D-glucopyranosyl chloride
• 英文别名: 2,3,4,6-tri-O-benzyl-α-D-glucopyranosyl chloride；(2R,3R,4R,5R,6R)-4,5-Bis(benzyloxy)-6-((benzyloxy)methyl)-2-chlorotetrahydro-2H-pyran-3-ol；(2R,3R,4R,5R,6R)-2-chloro-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• CAS: 74372-91-1
• 化学式: C₂₇H₂₉ClO₅
• 分子量: 468.977
• InChiKey: BMILQMXMRGETSQ-ACFIUOAZSA-N

物化性质

• 沸点：
  611.4±55.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-α-D-glucopyranosyl chloride 在 bis(cyclopentadienyl)-titanium(III) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以94%的产率得到3,4,6-三苄氧基-D-葡萄烯糖
  参考文献：
  名称：

  Rapid Preparation of Variously Protected Glycals Using Titanium(III)

  摘要：

  Glycosyl chlorides and bromides can be rapidly converted to glycals in high yield by reaction with (Cp2Ti[III]Cl)(2). This reagent tolerates a wide range of common carbohydrate protecting groups, including silyl ethers, acetals, and esters; the methodology provides a general route for the preparation of glycals substituted with both acid- and base-labile functionality. A reaction mechanism is proposed that is based on heteroatom abstraction to give an intermediate glycosyl radical. This radical reacts with a second equivalent of Ti(III) to yield a glycosyltitanium(IV) species. P-Heteroatom elimination from the glycosyltitanium(IV) complex gives the glycal.

  DOI：

  10.1021/jo982447k
• 作为产物：
  描述：

  3,4,6-tri-O-benzyl-D-glucopyranose 生成 3,4,6-tri-O-benzyl-α-D-glucopyranosyl chloride
  参考文献：
  名称：

  Rapid Preparation of Variously Protected Glycals Using Titanium(III)

  摘要：

  Glycosyl chlorides and bromides can be rapidly converted to glycals in high yield by reaction with (Cp2Ti[III]Cl)(2). This reagent tolerates a wide range of common carbohydrate protecting groups, including silyl ethers, acetals, and esters; the methodology provides a general route for the preparation of glycals substituted with both acid- and base-labile functionality. A reaction mechanism is proposed that is based on heteroatom abstraction to give an intermediate glycosyl radical. This radical reacts with a second equivalent of Ti(III) to yield a glycosyltitanium(IV) species. P-Heteroatom elimination from the glycosyltitanium(IV) complex gives the glycal.

  DOI：

  10.1021/jo982447k

文献信息

• Light-Mediated Cross-Coupling of Anomeric Trifluoroborates
  作者：Eric M. Miller、Maciej A. Walczak

  DOI：10.1021/acs.orglett.1c01035

  日期：2021.6.4

  Stereoselective reactions at the anomeric carbon constitute the cornerstone of preparative carbohydrate chemistry. Here, we report stereoselective C-arylation and etherification reactions of anomeric trifluoroborates derived from BMIDA esters. These reactions are characterized by high anomeric selectivities for 2-deoxysugars and broad substrate scope (24 examples), including disaccharides and trifluoroborates

  异头碳的立体选择性反应构成制备碳水化合物化学的基石。在这里，我们报告了衍生自 BMIDA 酯的异头三氟硼酸盐的立体选择性 C-芳基化和醚化反应。这些反应的特点是对 2-脱氧糖具有高异头选择性和广泛的底物范围（24 个例子），包括具有游离羟基的二糖和三氟硼酸盐。总之，这种新型碳水化合物试剂增加了适用于有效安装 C-C 键的异头亲核试剂的调色板。
• Highly Stereospecific Cross-Coupling Reactions of Anomeric Stannanes for the Synthesis of C-Aryl Glycosides
  作者：Feng Zhu、Michael J. Rourke、Tianyi Yang、Jacob Rodriguez、Maciej A. Walczak

  DOI：10.1021/jacs.6b07891

  日期：2016.9.21

  We demonstrate that configurationally stable anomeric stannanes undergo a stereospecific cross-coupling reaction with aromatic halides in the presence of a palladium catalyst with exceptionally high levels of stereocontrol. In addition to a broad substrate scope (>40 examples), this reaction eliminates critical problems inherent to nucleophilic displacement methods and is applicable to (hetero)aromatics

  我们证明，在具有极高立体控制水平的钯催化剂存在下，构型稳定的异头锡烷与芳族卤化物发生立体定向交叉偶联反应。除了广泛的底物范围（> 40 个例子）之外，该反应消除了亲核置换方法固有的关键问题，适用于（杂）芳烃、肽、药物、常见单糖和含有游离羟基的糖类。
• Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl <i>C</i>-Glycosides
  作者：Feng Zhu、Jacob Rodriguez、Tianyi Yang、Ilia Kevlishvili、Eric Miller、Duk Yi、Sloane O’Neill、Michael J. Rourke、Peng Liu、Maciej A. Walczak

  DOI：10.1021/jacs.7b08707

  日期：2017.12.13

  highly stereospecific reaction of anomeric nucleophiles. First, methods for the preparation of anomeric stannanes have been developed and optimized to afford both anomers of common saccharides in high anomeric selectivities. We established that oligosaccharide stannanes could be prepared from monosaccharide stannanes via O-glycosylation with Schmidt-type donors, glycal epoxides, or under dehydrative

  糖类 C1 异头位置的立体选择性操作是制备性碳水化合物化学的核心目标之一。从历史上看，大多数与异头碳形成键的反应都集中在亲核试剂与带有离去基团的糖供体的反应上。在这里，我们描述了一种利用异头亲核试剂的高度立体特异性反应立体选择性合成 C-芳基糖苷的新方法。首先，已经开发并优化了制备异头锡烷的方法，以高异头选择性提供常见糖类的两种异头异构体。我们确定寡糖锡烷可以从单糖锡烷通过与施密特型供体、糖基环氧化物的 O-糖基化或在脱水条件下与 C1 醇制备。第二，我们确定了一组通用的催化条件，其中 Pd2(dba)3 (2.5 mol%) 和一个庞大的配体 (JackiePhos, 10 mol%) 控制了 β-消除途径。我们证明了糖基交叉偶联对具有单糖和低聚糖、脱氧糖、具有游离羟基的糖类、吡喃糖和呋喃糖底物的两种异头异构体产生始终如一的高异头选择性。在 Salmochelins（铁载体）和商业抗糖尿
• Zinc p-tert-butylbenzoate catalyzed glycosylation with glycopyranosyl chloride.
  作者：Mugio NISHIZAWA、Dulce M. GARCIA、Toshiyuki SHIN、Hidetoshi YAMADA

  DOI：10.1248/cpb.41.784

  日期：——

  A 0.1 eq of zinc p-tert-butylbenzoate significantly accelerates glycosylation of alcohol with glycopyranosyl chloride in the presence of 2-methyl-2-butene to give β-glycoside in high yield with fair to good β-selectivity.

  0.1当量的锌对叔丁基苯甲酸酯显著加速了醇与甘露糖苷氯化物的糖苷化反应，且在2-甲基-2-丁烯的存在下，产生了高产率且良好至公平的β选择性β-糖苷。
• Direct Coupling of Amides and Urea to Glycosyl Halides Using Silver Triflate
  作者：Luz M. Rosado、Terence J. Meyerhoefer、Saqib M. Bett、Saba. Ilyas、Lubabalo. Bululu、Carla A. Martin、Troy W. Joseph、Michael De Castro

  DOI：10.1002/ejoc.201600350

  日期：2016.6

  We herein report the coupling of various amides and ureas to glycosyl halides in the presence of silver triflate at room temperature. A 1:1 mixture of α/β diastereomers was obtained when alkyl/heteroaryl amides and substituted ureas were added to gluco and galacto haloglycosides. The effect of temperature, halogen, protecting group of the sugar and substituent of the amide in the overall yields and

  我们在此报告了在室温下在三氟甲磺酸银存在下各种酰胺和脲与糖基卤化物的偶联。当将烷基/杂芳基酰胺和取代的脲加入葡糖和半乳糖卤代糖苷时，得到 1:1 的 α/β 非对映体混合物。还探讨了温度、卤素、糖的保护基团和酰胺的取代基对反应的总产率和立体选择性的影响。当在反应中使用乙酰保护的葡萄糖醛酸酰胺时，在室温下以良好的收率获得了相应假双糖的β端基异构体作为主要异构体。使用 HeLa 癌细胞对新合成的化合物进行了活力研究。本研究还讨论了获得的结果。