methyl 2,4-di-O-benzyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-α-L-rhamnopyranoside | 71348-35-1

• 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: methyl 2,4-di-O-benzyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-α-L-rhamnopyranoside
• 英文别名: methyl 2,4-di-O-benzyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhanmopyranosyl)-α-L-rhamnopyranoside；methyl 3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-2,4-di-O-benzyl-α-L-rhamnopyranoside；[(2S,3S,4R,5R,6S)-4,5-diacetyloxy-6-[(2R,3R,4R,5S,6S)-2-methoxy-6-methyl-3,5-bis(phenylmethoxy)oxan-4-yl]oxy-2-methyloxan-3-yl] acetate
• CAS: 71348-35-1
• 化学式: C₃₃H₄₂O₁₂
• 分子量: 630.689
• InChiKey: CUPBOUOLDUMUCS-UZPTXNNVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  45.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  134.28
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  methyl 2,4-di-O-benzyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-α-L-rhamnopyranoside 在 sodium methylate 、 sodium hydride 、 对甲苯磺酸 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.0h， 生成 (3aR,4S,6S,7S,7aR)-7-Allyloxy-4-((2R,3R,4R,5S,6S)-3,5-bis-benzyloxy-2-methoxy-6-methyl-tetrahydro-pyran-4-yloxy)-2,2,6-trimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran
  参考文献：
  名称：

  Mukherjee, Atreyee; Roy, Nirmolendu, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1994, vol. 33, # 8, p. 726 - 728

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 4-O-benzyl-2,3-O-isopropylidene-α-L-rhamnopyranoside 在 sodium hydroxide 、 4 A molecular sieve 、 四丁基溴化铵 、 氰化汞 、 溶剂黄146 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 28.0h， 生成 methyl 2,4-di-O-benzyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-α-L-rhamnopyranoside
  参考文献：
  名称：

  Mukherjee, Atreyee; Roy, Nirmolendu, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1994, vol. 33, # 8, p. 726 - 728

  摘要：

  DOI：

文献信息

• Synthesis and 13C-NMR spectroscopic investigations of rhamnobioses
  作者：András Lipták、Pál Nánási、András Neszmélyi、Hildebert Wagner

  DOI：10.1016/0040-4020(80)87028-1

  日期：1980.1

  for the synthesis of all mono- and di-O-benzyl ethers of methyl α-L-rhamnopyranoside applying a new stereoselective method for the hydrogenolytic ring-cleavage of benzylidene acetals. Using the prepared dibenzyl ethers as aglycones, the (1→2)-, (1→3)- and (l→4)-linked rhamnosyl-rhamnose derivatives (13–15) were synthesised. Hydrogenolysis of the latter compounds and subsequent acetylation gave the

  已经开发了一种方便的方法，该方法使用新的立体选择性方法对亚苄基乙缩醛进行氢解环裂解，来合成甲基α-L-鼠李吡喃糖苷的所有单-和二-O-苄基醚。使用制备的二苄醚作为糖苷配基，所述（1→2） - ，（1→3） -和（1→4） -连接的鼠李糖鼠李糖衍生物（13 - 15）的合成。后者化合物的氢解和随后的乙酰化，得到五乙酸盐（16 - 18）甲基dirhamnosides，其在皂化提供的免费甲基dirhamnosides（的19 - 21）。16 – 18的乙酰化作用得到相应的去氧己糖六乙酸酯，其通过皂化转化为三种二糖。通过13 C-NMR光谱研究每种产物的结构，并且出于13 C-NMR研究的目的，甲基α-L-鼠李糖吡喃糖苷的单-O-甲基醚，甲酸酯的二乙酸酯和二-O-苄基醚。合成了这些化合物，以及甲基α-L-鼠李吡喃糖苷的二乙酸酯。
• Synthetic oligosaccharides related to Group B streptococcal polysaccharides. The rhamnotriose moiety of the common antigen
  作者：Vince Pozsgay、Jean-Robert Brisson、Harold J. Jennings

  DOI：10.1139/v87-459

  日期：1987.12.1

  The methyl glycoside (1) of the α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → portion of the group-specific, common antigen polysaccharide of Group B Streptococci has been synthesized. The key compound of the synthesis was methyl 3,4-di-O-benzyl-α-L-rhamnopyranoside (4). Controlled acetolysis of 4 gave 1,2-di-O-acetyl-3,4-di-O-benzyl-α-L-rhamnopyranose (10), which upon reaction with 4 under catalysis

  α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → 2)-α-L-Rhap-(1 → 部分组特异性、共同抗原)的甲基糖苷(1)已经合成了 B 族链球菌的多糖。合成的关键化合物是甲基 3,4-二-O-苄基-α-L-吡喃鼠李糖苷 (4). 4 的受控乙酰水解得到 1,2-二-O-乙酰基-3,4-二-O-苄基-α-L-吡喃鼠李糖 (10)，在三氟甲磺酸三甲基甲硅烷基酯 (TMS-Tf) 的催化下与 4 反应生成 α-(1 → 2)-连接的二鼠李糖苷。然后去保护得到 1. TMS-Tf 也用于与四-O-乙酰基-α-L-鼠李糖基化反应中。发现受体醇的乙酰化是 TMS-Tf 辅助糖基化中的主要副反应。一-维核 Overhauser 增强差分光谱表明，在解决方案中，1 占据弯曲而不是扩展构象。
• Synthesis and 13C-n.m.r. spectroscopic investigation of three methyl rhamnotriosides
  作者：András Lipták、János Harangi、Gyula Batta、Otto Seligmann、Hildebert Wagner

  DOI：10.1016/0008-6215(84)85401-4

  日期：1984.8

  Abstract Methyl 2,3-O-isopropylidene-4-O-(2,3-O-isopropylidene-α- l -rhamnopyranosyl)- α- l -rhamnopyranoside, methyl 2,4-di-O-benzyl-3-O-(2,3-O-isopropylidene- α- l -rhamnopyranosyl)-α- l -rhamnopyranoside, and methyl 3,4-di-O-benzyl-2-O- (2,3-O-isopropylidene-α- l -rhamnopyranosyl)-α- l -rhamnopyranoside, obtained by isopropylidenation of the respective methyl rhamnobiosides, were glycosylated with

  摘要2,3-O-异亚丙基-4-O-（2,3-O-异亚丙基-α-1-鼠李糖基吡喃糖基）-α-1-l-鼠李糖吡喃糖苷，甲基2,4-二-O-苄基-3-O -（2,3-O-异亚丙基-α-1-鼠李吡喃糖基）-α-1-鼠李吡喃糖苷和甲基3,4-二-O-苄基-2-O-（2,3-O-异亚丙基-α-通过各个甲基鼠李糖苷的异丙基化获得的1-鼠李糖吡喃糖基）-α-1-鼠李糖吡喃糖苷被2,3,4-三-O-乙酰基-α-1-鼠李糖吡喃糖基溴化物糖基化。从产物中除去保护基，得到α-1-Rhap-（1→4）-α-1-Rhap-（1→4）-α-1-Rhap，α-1-Rhap-（ 1→4）-α-l-Rhap-（1→3）-α-l-Rhap和α-1-Rhap-（1→4）-α-l-Rhap-（1→2）-α- l -Rhap。这些三糖苷及其七乙酸盐已通过13C-nmr光谱法进行了研究。
• Synthesis of methyl 3-O-(2-O-methyl-α-l-fucopyranosyl)-α-l-rhamnopyranoside, methyl 3-O-α-l-rhamnopyranosyl-α-d-glucopyranoside, and methyl 3-O-[3-O-(2-O-methyl-α-l-fucopyranosyl)-α-l-rhamnopyranosyl]-α-l-rhamnopyranoside: di- and tri-saccharide segments of a lipo-oligosaccharide (LOS-1) of Mycobacterium szulgai
  作者：Mukund K. Gurjar、Prathama S. Mainkar

  DOI：10.1016/0008-6215(93)84227-w

  日期：1993.2
• Synthesis of methyl 3--[3--(2,3,4-tri--methyl-α-L-rhamnopyranosyl)-α-L-rhamnopyranosyl]-α-L-rhamnopyranoside : The outer trisaccharide unit of a unique glycopeptidolipid
  作者：Mukund K Gurjar、Anupama S Mainkar

  DOI：10.1016/s0040-4020(01)80018-1

  日期：1992.1

  The combination of sugars present in Mycobacterium xenopi glycopeptidolipid (GPL X-1) has been characterised as O-(2,3,4-tri-O-methyl-alpha-L-rhamnopyranosyl)-(1-3)-O-(alpha-L-rhamnopyranosyl)-(1-3)-O-(alpha-L-rhamnopyranosyl)-(1-3)-6-deoxy-L-glucose. Two synthetic routes (A and B) towards the outer trisaccharide segment (2) have been designed. Route A involved the condensation of the aglycone (7) with 2,3,4-tri-O-acetyl-alpha-L-rhamnopyranosyl bromide (13) to afford which was sequentially deacetylated, methylated, deallylated and reacetylated to afford 12. Condensation of 12 with 16 in the presence of borontrifluoride etherate was unsuccessful. In route B, the disaccharide 21 was synthesised by the coupling reaction between 16 and 18 in the presence of borontrifluoride-etherate followed by deallylation. Alternatively, the disaccharide triacetate (22) was first prepared and routine modifications on it led to the formation of 21. Final condensation of 21 with the trichloroacetimidate (29) followed by sequential deacetylation, methylation and debenzylation afforded the trisaccharide (2).