2,3,4-tri-O-benzyl-α-L-rhamnopyranosyl bromide | 59055-61-7

• 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: 2,3,4-tri-O-benzyl-α-L-rhamnopyranosyl bromide
• 英文别名: (2S,3R,4R,5S,6S)-2-bromo-6-methyl-3,4,5-tris(phenylmethoxy)oxane
• CAS: 59055-61-7
• 化学式: C₂₇H₂₉BrO₄
• 分子量: 497.429
• InChiKey: MJZXQAVNDOYDAP-CMKGNXEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-benzyl-α-L-rhamnopyranosyl bromide 在 Ag-silicate Wilkinson's catalyst 、 3 A molecular sieve 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 反应 11.0h， 生成 Benzyl-4-O-benzyl-3-O-(2,3,4-tri-O-benzyl-β-L-rhamnopyranosyl)-α-L-rhamnopyranosid
  参考文献：
  名称：

  Paulsen, Hans; Kutschker, Wolfram; Lockhoff, Oswald, Chemische Berichte, 1981, vol. 114, # 10, p. 3233 - 3241

  摘要：

  DOI：
• 作为产物：
  描述：

  Benzyl-2,3,4-tri-O-benzyl-β-L-rhamnopyranosid 在 盐酸 、 氢溴酸 作用下， 以 1,4-二氧六环 、 吡啶 、 二氯甲烷 为溶剂， 反应 42.07h， 生成 2,3,4-tri-O-benzyl-α-L-rhamnopyranosyl bromide
  参考文献：
  名称：

  Paulsen, Hans; Kutschker, Wolfram; Lockhoff, Oswald, Chemische Berichte, 1981, vol. 114, # 10, p. 3233 - 3241

  摘要：

  DOI：

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
• Synthese von β-l-rhamnosidisch verknüpften oligosacchariden des lipopolysaccharides aus Shigella flexneri sero-typ 6
  作者：Hans Paulsen、Wolfram Kutschker

  DOI：10.1016/0008-6215(83)88004-5

  日期：1983.8

  O -β- l -rhamnopyranosyl-(1→2)- l -rhamnopyranose ( 21 ) is described. The latter structure has been proposed as the repeating unit of the O-specific side-chain of the lipopolysaccharide obtained from Shigella flexneri Serotype 6. The key-intermediate was 4- O -acetyl-2- O -allyl-3- O -benzyl-α- d -rhamnopyranosyl bromide, which was first linked to benzyl 3,4-di- O -benzyl-α- l -rhamnopyranoside,

  摘要三糖O-β-1-鼠李吡喃糖基-（1→4）-O-β-1-鼠李吡喃糖基-（1→2）-1-鼠李吡喃糖（14）和四糖O-（2-乙酰胺基- 2-脱氧-β-d-吡喃并吡喃糖基）-（1→2）-O- [β-1-鼠李糖吡喃糖基-（1→4）]-O-β-1-鼠李糖吡喃糖基-（1→2）-l-鼠李糖吡喃糖（21）被描述。已提出后者的结构作为得自弗氏志贺氏菌血清型6的脂多糖的O-特异性侧链的重复单元。关键中间体为4-O-乙酰基-2-O-烯丙基-3-O-苄基。首先与苄基3，4-二-O-苄基-α-1-鼠李糖吡喃糖苷连接的-α-d-鼠李糖吡喃糖基溴化物得到封闭的β-连接的二糖。将其O-脱乙酰化，并在O-4'处与2,3,4-三-O-苄基-α-1-鼠李糖基吡喃糖基溴偶联，得到苄基O-（2,3，4-三-O-苄基-β-1-鼠李糖基吡喃糖基）-（1→4）-O-（2-O-烯丙基-3-O-苄基-β-1-鼠李糖吡喃糖基）-（1→2）-3
• Synthesis and antitumor activity of quaternary ellipticine glycosides, a series of novel and highly active antitumor agents
  作者：Tadashi Honda、Mika Kato、Minako Inoue、Tetsuo Shimamoto、Keiyuu Shima、Toshihiro Nakanishi、Takako Yoshida、Teruhisa Noguchi

  DOI：10.1021/jm00402a007

  日期：1988.7

  A series of ellipticine glycosides [2-N-glycosyl quaternary pyridinium salts of three ellipticines: ellipticine (1), 9-methoxyellipticine (2), and 9-hydroxyellipticine (4)] were stereoselectively synthesized in good yields by an improved condensation reaction between ellipticines [1, 2, and 9-acetoxyellipticine (3)] and protected (peracylated and perbenzylated) glycosyl halides with cadmium carbonate, followed by deprotection. These glycosides were preliminarily evaluated for their antitumor activity in the L1210 leukemia system. Twenty-six (53%) of the 49 glycosides tested were curative, and five [9-hydroxyellipticine L-arabinopyranoside (41b), D-lyxofuranoside (43a), L-lyxopyranoside (44b), D-xylofuranoside (49a), and L-rhamnopyranoside (56)] were selected for extended evaluation on the basis of their high levels of activity. The structure-activity relationships are discussed. The selected glycosides showed remarkable activity in six different murine tumor systems with excellent therapeutic ratios; their efficacy surpassed that of doxorubicin against three of these systems. On the basis of these results and ease of formulation, the two glycosides 41b (SUN4599) and 49a (SUN5073) were selected for further preclinical evaluation and possible clinical development.
• Synthesis of di- and tri-saccharides related to the polysaccharide from Streptococcus pneumoniae type 23 and a study of their inhibition in the precipitin reaction
  作者：Asim K. Ray、Usha B. Maddali、Abhijit Roy、Nirmolendu Roy

  DOI：10.1016/0008-6215(90)84132-e

  日期：1990.3

  Syntheses of methyl 2-O-beta-L-rhamnopyranosyl-beta-D-galactopyranoside (9), methyl 2-O-alpha-L-rhamnopyranosyl-beta-D-galactopyranoside (13), and methyl 4-O-beta-D-glucopyranosyl-2-O-alpha-L-rhamnopyranosyl-beta-D- galactopyranoside (16) in good yields are described. Both 13 and 16 significantly inhibit antigen-antibody precipitation in the S. pneumoniae Type 23 immune system. The results indicate that the rhamnosyl group in the side chain of the repeating unit of the antigen is alpha and not beta as reported previously, and that the trisaccharide related to 16 is the immunodominant group.
• Kamiya, Shintaro; Esaki, Sachiko; Shiba, Naoko, Agricultural and Biological Chemistry, 1987, vol. 51, p. 2207 - 2214
  作者：Kamiya, Shintaro、Esaki, Sachiko、Shiba, Naoko

  DOI：——

  日期：——