2,3:4,6-di-O-isopropylidenemannopyranosyl bromide | 224778-46-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 2,3:4,6-di-O-isopropylidenemannopyranosyl bromide
• 英文别名: (1R,2S,6S,7R,9R)-7-bromo-4,4,12,12-tetramethyl-3,5,8,11,13-pentaoxatricyclo[7.4.0.02,6]tridecane
• CAS: 224778-46-5
• 化学式: C₁₂H₁₉BrO₅
• 分子量: 323.184
• InChiKey: PCCKVHFQQGOZOW-ZJDVBMNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3:4,6-di-O-isopropylidenemannopyranosyl bromide 在 bis(cyclopentadienyl)-titanium(III) chloride 作用下， 以 苯 为溶剂， 反应 0.5h， 以90%的产率得到4,6-O-异亚丙基-D-葡萄糖醛
  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：

  1-O-acetyl-2,3:4,6-di-O-isopropylidenemannopyranose 在 三甲基溴硅烷 作用下， 以 二氯甲烷 为溶剂， 生成 2,3:4,6-di-O-isopropylidenemannopyranosyl bromide
  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

• Visible-Light-Induced Pd-Catalyzed Radical Strategy for Constructing <i>C</i>-Vinyl Glycosides
  作者：Ming Li、Yi-Feng Qiu、Cui-Tian Wang、Xue-Song Li、Wan-Xu Wei、Yu-Zhao Wang、Qiao-Fei Bao、Ya-Nan Ding、Wei-Yu Shi、Yong-Min Liang

  DOI：10.1021/acs.orglett.0c02053

  日期：2020.8.21

  visible-light-induced palladium-catalyzed Heck reaction for bromine sugars and aryl olefins with high regio- and stereochemistry selectivity for the preparation of C-glycosyl styrene is described. This reaction takes place in one step at room temperature by using a simple and readily available starting material. This protocol can be scaled up to a wide range of glycosyl bromide donors and aryl olefin substrates

  描述了一种新型可见光诱导的钯催化的溴糖和芳基烯烃的 Heck 反应，具有高区域和立体化学选择性，用于制备C-糖基苯乙烯。该反应使用简单易得的起始原料在室温下一步发生。该方案可以扩展到广泛的糖基溴供体和芳基烯烃底物。机理研究表明涉及自由基加成途径。
• “Boomerang” Strategy in Carbohydrate Chemistry: Diastereoselective Synthesis of <i>C</i>-Glycosylated Benzothiazoles from <i>ortho</i>-Isocyanophenyl Thioglycosides
  作者：Li-Yan Hu、Shen-Yuan Zhang、Li Zhu、Yang Li、Kai Luo、Lei Wu

  DOI：10.1021/acs.orglett.3c03817

  日期：2024.1.12