3,4,6-tri-O-acetyl-2-bromo-2-deoxy-α-D-galactopyranosyl bromide | 152376-76-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3,4,6-tri-O-acetyl-2-bromo-2-deoxy-α-D-galactopyranosyl bromide
• 英文别名: tri-O-acetyl-2-bromo-2-deoxy-α-D-galactopyranosyl bromide；Tri-O-acetyl-2-brom-2-desoxy-α-D-galactopyranosylbromid；[(2R,3S,4S,5R,6R)-3,4-diacetyloxy-5,6-dibromooxan-2-yl]methyl acetate
• CAS: 152376-76-6
• 化学式: C₁₂H₁₆Br₂O₇
• 分子量: 432.063
• InChiKey: NTYSKQNPDDHOBU-ZIQFBCGOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 氯仿 、 溴 作用下， 生成 3,4,6-tri-O-acetyl-2-bromo-2-deoxy-α-D-galactopyranosyl bromide
  参考文献：
  名称：

  Gachokidse, Zhurnal Obshchei Khimii, 1940, vol. 10, p. 507,508, 509

  摘要：

  DOI：

文献信息

• Structural and Computational Analysis of 2‐Halogeno‐Glycosyl Cations in the Presence of a Superacid: An Expansive Platform
  作者：Ludivine Lebedel、Ana Ardá、Amélie Martin、Jérôme Désiré、Agnès Mingot、Marialuisa Aufiero、Nuria Aiguabella Font、Ryan Gilmour、Jesus Jiménez‐Barbero、Yves Blériot、Sébastien Thibaudeau

  DOI：10.1002/anie.201907001

  日期：2019.9.23

  derivatives display intramolecular stabilization of the glycosyl cations. Introducing a strongly electron-withdrawing fluorine atom at C2 exerts considerable influence on the oxocarbenium ion reactivity. In a superacid, these oxocarbenium ions are quenched by weakly coordinating SbF6 - anions, thereby demonstrating their highly electrophilic character and their propensity to interact with poor nucleophiles

  公开了基于天然核糖核酸的结构分析，该结构难以分析的糖基阳离子来自超酸中的天然和非天然单糖。首次有可能探索缩合相中一系列2-卤代葡萄糖基，半乳糖基和甘露糖基供体中C2位置的脱氧和卤素取代的结果。使用DFT计算支持的低温原位NMR实验对这些阳离子中间体进行了表征。2-溴衍生物显示糖基阳离子的分子内稳定。在C 2引入强吸电子的氟原子对氧碳鎓离子反应性产生相当大的影响。在过酸中，这些氧碳鎓离子通过弱配位的SbF6-阴离子而淬灭，
• Bromination of 1,5-Anhydrohex-1-enitols (Glycals) Using Quaternary Ammonium Tribromides as Bromine Donors: Synthesis of α-1,2-<i>trans</i>-2-Bromo-2-deoxyglycopyranosyl Bromides and Fluorides
  作者：Marcus Teichmann、Gérard Descotes、Dominique Lafont

  DOI：10.1055/s-1993-25964

  日期：——

  Addition of bromine to glycals using quaternary ammonium tribromides as bromine donors is realized with higher stereoselectivities (α-1,2-trans configurated products) compared to bromination with molecular bromine. The reaction is neither sensitive to the solvent nor to the nature of the protecting groups (acetyl, benzoyl, benzyl) of the glycals and very slightly affected by the orientation of the substituents of the different glycals. Some of the α-1, 2-trans dibromo adducts have been isolated in 60-75% yields and transformed into the corresponding α-1,2-trans-2-bromo-2-deoxyglycopyranosyl fluorides.

  与使用分子溴进行溴化相比，使用季铵三溴化物作为溴给体将溴加到糖醛中具有更高的立体选择性（δ-1,2-反式构型产物）。该反应对溶剂和糖醛保护基（乙酰基、苯甲酰基、苄基）的性质都不敏感，受不同糖醛取代基方向的影响也很小。一些δ-1,2-反式二溴加合物的分离率为 60-75%，并可转化为相应的δ-1,2-反式-2-溴-2-脱氧吡喃糖基氟化物。
• Electrochemical Bromination of Peracetylated Glycals
  作者：Marija Čolović、Mirjana Vukićević、Dejan Šegan、Dragan Manojlović、Neso Sojic、László Somsák、Rastko D. Vukićević

  DOI：10.1002/adsc.200700310

  日期：2008.1.4

  Bromination of glycals with tribromides formed in situ from bromine and different bromide salts in dichloromethane (DCM) or acetonitrile (AN) was found to give predominantly the products of anti addition of bromine from the C-6 side in high yields. The same selectivity, which was much higher compared to bromination with bromine alone, was achieved in bromination of these substrates by anodic generation

  发现在二氯甲烷（DCM）或乙腈（AN）中，由溴和不同溴化物盐在原位形成的三溴化物对溴化物的溴化作用，主要产生了高收率的C-6侧溴的反加成产物。通过由相同的盐阳极生成溴，在这些底物的溴化中，实现了与仅用溴进行溴化相比具有更高的相同选择性。