3,4,6-tri-O-acetyl-2-O-benzyl-α-D-galactopyranosyl bromide | 53872-78-9

• 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-O-benzyl-α-D-galactopyranosyl bromide
• 英文别名: [(2R,3S,4S,5R,6R)-3,4-diacetyloxy-6-bromo-5-phenylmethoxyoxan-2-yl]methyl acetate
• CAS: 53872-78-9
• 化学式: C₁₉H₂₃BrO₈
• 分子量: 459.291
• InChiKey: BDEKKKJMOUBAPE-SPOLIRPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-O-benzyl-α-D-galactopyranosyl bromide 在 palladium on activated charcoal 4 A molecular sieve 、 氢气 、 silver trifluoromethanesulfonate 作用下， 以 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 20.0 ℃ 、1.38 MPa 条件下， 反应 16.0h， 生成
  参考文献：
  名称：

  Effects of Lipid Chain Lengths in α-Galactosylceramides on Cytokine Release by Natural Killer T Cells

  摘要：

  Glycolipid presentation by CD1 proteins has emerged as an important aspect of antigen recognition, and presentation of alpha-glycosylceramides by CD1d to natural killer T cells has become a central focus in understanding how glycolipid presentation can influence immune responses. An alpha-galactosylceramide containing relatively long lipid chains has been the subject of intense study because, when presented by CD1d to natural killer T cells, it stimulates the release of both proinflammatory and immunomodulatory cytokines. Using an efficient synthesis of alpha-galactosylceramides, we have prepared a series of glycolipids in which the lipid chain lengths have been incrementally varied. The responses of natural killer T cells to these glycolipids have been determined, and we have found that truncation of the phytosphingosine lipid chain increases the relative amounts of immunomodulatory cytokines released. In similar fashion, the length of the acyl chain in alpha-galactosylceramides influences cytokine release profiles.

  DOI：

  10.1021/ja045385q
• 作为产物：
  描述：

  1,3,4,6-Tetra-O-acetyl-2-O-benzyl-D-galactopyranose 在 氢溴酸 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以75%的产率得到3,4,6-tri-O-acetyl-2-O-benzyl-α-D-galactopyranosyl bromide
  参考文献：
  名称：

  Effects of Lipid Chain Lengths in α-Galactosylceramides on Cytokine Release by Natural Killer T Cells

  摘要：

  Glycolipid presentation by CD1 proteins has emerged as an important aspect of antigen recognition, and presentation of alpha-glycosylceramides by CD1d to natural killer T cells has become a central focus in understanding how glycolipid presentation can influence immune responses. An alpha-galactosylceramide containing relatively long lipid chains has been the subject of intense study because, when presented by CD1d to natural killer T cells, it stimulates the release of both proinflammatory and immunomodulatory cytokines. Using an efficient synthesis of alpha-galactosylceramides, we have prepared a series of glycolipids in which the lipid chain lengths have been incrementally varied. The responses of natural killer T cells to these glycolipids have been determined, and we have found that truncation of the phytosphingosine lipid chain increases the relative amounts of immunomodulatory cytokines released. In similar fashion, the length of the acyl chain in alpha-galactosylceramides influences cytokine release profiles.

  DOI：

  10.1021/ja045385q

文献信息

• Diastereoselective sp³ C–O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols
  作者：Fei Yu、Jalen L. Dickson、Ravi S. Loka、Hengfu Xu、Richard N. Schaugaard、H. Bernhard Schlegel、Long Luo、Hien M. Nguyen

  DOI：10.1021/acscatal.0c01470

  日期：2020.6.5

  electrophiles to control α-1,2-cis selectivity. In our approach, earth-abundant copper not only acts as a photocatalyst and a bond-forming catalyst, but also enforces the stereocontrolled formation of anomeric C–O bonds. This cross-coupling protocol enables highly diastereoselective access to a wide variety of α-1,2-cis-glycosides and biologically relevant α-glycan oligosaccharides. Our work provides a foundation

  铜催化的交叉偶联反应已成为产生碳-杂原子键（许多有机分子的重要框架）的最有效方法之一。但是，由于铜的氧化加成反应迟钝，铜催化的卤代烷与烷基醇的C（sp 3）–O交叉偶联仍然难以实现。为解决这一挑战，我们开发了一种催化铜系统，该系统可借助可见光克服铜的氧化加成障碍，并有效地促进糖基溴化物与脂肪族醇的交叉偶联，从而提供具有C（sp 3）-O键的高非对映选择性。重要的是，该催化体系导致温和而有效的立体选择性构建α-1,2-顺式的方法苷，这是最重要的，但具有挑战性。通常，α-1,2-顺式糖苷C–O键形成过程中的立体化学结果是无法预测的，并且取决于与碳水化合物偶联伙伴结合的保护基的空间和电子性质。当前，最可靠的方法依赖于在碳水化合物亲电体的C2和C4位置使用手性辅助或氢键引导基团来控制α-1,2-顺式选择性。在我们的方法中，富含地球的铜不仅充当光催化剂和形成键的催化剂，而且还增强了异头C-O键的立体
• Versatile Synthesis and Mechanism of Activation of <i>S</i>-Benzoxazolyl Glycosides
  作者：Medha N. Kamat、Nigam P. Rath、Alexei V. Demchenko

  DOI：10.1021/jo0711844

  日期：2007.8.31

  As a part of a program for developing new efficient procedures for stereoselective glycosylation, a range of S-benzoxazolyl (SBox) glycosides have been synthesized. The mechanistic aspects of the SBox moiety activation for glycosylation via a variety of conceptually different pathways in the presence of thiophilic, electrophilic, or metal-based promoters have been investigated.

  作为开发用于立体选择性糖基化的新有效方法的程序的一部分，已合成了一系列S-苯并恶唑基（SBox）糖苷。已经研究了在存在基于硫的，亲电子的或基于金属的启动子的情况下经由各种概念上不同的途径进行糖基化的SBox部分活化的机械方面。
• Reductive decomplexation of biscobalthexacarbonyl acetylenes into olefins
  作者：Seijiro Hosokawa、Minoru Isobe

  DOI：10.1016/s0040-4039(98)00281-0

  日期：1998.4

  found other reductive conditions with endo-cyclic complexes, and recently other reductive conditions with both endo- and exo-cyclic complexes using either tributyltin hydride or triethylsilane. The original acetylene derivatives transformed selectively either into the corresponding cis olefins or cis-vinylsilanes.

  乙炔二钴六羰基配合物的分解通常可以在氧化条件下进行。我们发现了使用内环配合物的其他还原条件，最近发现了使用氢化三丁基锡或三乙基硅烷的同时具有内环和外环配合物的其他还原条件。原始乙炔衍生物选择性地转化为相应的顺式烯烃或顺式乙烯基硅烷。
• <i>S</i>-Benzoxazolyl (SBox) Glycosides as Novel, Versatile Glycosyl Donors for Stereoselective 1,2-Cis Glycosylation
  作者：Alexei V. Demchenko、Nelli N. Malysheva、Cristina De Meo

  DOI：10.1021/ol0273452

  日期：2003.2.1

  [reaction: see text] Novel glycosyl donors, S-benzoxazolyl (SBox) glycosides, have been synthesized, tested toward various protecting group manipulations, and applied to the highly stereoselective 1,2-cis glycosylation. These compounds fulfill the requirements for a modern glycosyl donor such as accessibility, high stability toward protecting group manipulations, and mild activation conditions. It

  [反应：见正文]合成了新型糖基供体S-苯并恶唑基（SBox）糖苷，已针对各种保护基操作进行了测试，并将其应用于高度立体选择性的1,2-顺式糖基化。这些化合物满足了现代糖基供体的要求，例如可及性，对保护基操纵的高度稳定性以及温和的活化条件。还证明了SBox糖苷可以承受其他糖基供体的活化条件，因此可以使O-戊烯基和硫代糖苷发生选择性糖基化。
• Paulsen, Hans; Lockhoff, Oswald, Chemische Berichte, 1981, vol. 114, # 9, p. 3079 - 3101
  作者：Paulsen, Hans、Lockhoff, Oswald

  DOI：——

  日期：——