allyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside | 518975-31-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside
• 英文别名: [(2S,3S,4S,5R,6R)-4-benzoyloxy-5-hydroxy-2-methyl-6-prop-2-enoxyoxan-3-yl] benzoate
• CAS: 518975-31-0
• 化学式: C₂₃H₂₄O₇
• 分子量: 412.439
• InChiKey: JDMVETHOJRJXMZ-MRHQXCTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  allyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside 在 吡啶 、 sodium acetate 、 溶剂黄146 、 palladium dichloride 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成
  参考文献：
  名称：

  合成由α-（1→2）-和α-（1→3）连接的鼠李糖聚糖主链和GlcNAc侧链组成的寡糖的一般方法

  摘要：

  已经开发了用于合成由具有GlcNAc侧链的（1→2）-和（1→3）-连接的鼠李糖寡糖组成的寡糖的一般方法。例如，在植物致病性细菌丁香假单胞菌pv的脂多糖的O多糖部分中的两个十糖的高效且收敛的合成。获得了ribicola NCPPB 1010。这两个十糖分别由O多糖重复单元I + II和II + I组成。烯丙基3- ø -乙酰基-4- ö苯甲酰基α-L-吡喃鼠李糖苷，烯丙基2- ø -苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖苷，2,4-二- ö苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖三氯乙酰亚胺酯，和3- ö -乙酰基-2,4-二- ö苯甲酰基α-L-吡喃鼠李糖三氯乙酰亚胺酯，这是由高度选择性3-O-获得酰化用作关键合成子，以得到所需的具有3 3-和3 7-游离羟基的α-（1→2）-和α-（1→3）连接的鼠李糖单糖受体。因此，合成了几种二糖，然后由它们合成了四糖和六糖。六糖供

  DOI：

  10.1016/s0040-4020(03)00075-9
• 作为产物：
  描述：

  苯甲酰氯 、 allyl 4-O-benzoyl-α-L-rhamnopyranoside 在 二正丁基氧化锡 、 吡啶 作用下， 以 甲苯 为溶剂， 以71%的产率得到allyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of monomethylated dioscin derivatives and their antitumor activities

  摘要：

  All possible eight monomethylated dioscin derivatives (1-8) were synthesized. Their inhibitory activities against P388 and A-549 cells were determined, and the results indicate that six of the eight hydroxyls of dioscin are the 'key polar groupings' for tumor inhibitory activities. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(02)00443-3

文献信息

• β-Selective Glycosylation Using Axial-Rich and 2-<i>O</i>-Rhamnosylated Glucosyl Donors Controlled by the Protecting Pattern of the Second Sugar
  作者：Masafumi Bando、Yuri Kawasaki、Osamu Nagata、Yasunori Okada、Daiki Ikuta、Kazutada Ikeuchi、Hidetoshi Yamada

  DOI：10.1248/cpb.c20-00733

  日期：2021.1.1

  Herein, we describe two counterexamples of the previously reported β/α-selectivity of 96/4 for glycosylation using ethyl 2-O-[2,3,4-tris-O-tert-butyldimethylsilyl (TBS)-α-L-rhamnopyranosyl]-3,4,6-tris-O-TBS-thio-β-D-glucopyranoside as the glycosyl donor. Furthermore, we investigated the effects of protecting group on the rhamnose moieties in the glycosylation with cholestanol and revealed that β-selectivity originated from the two TBS groups at the 3-O and 4-O positions of rhamnose. In contrast, the TBS group at the 2-O position of rhamnose hampered the β-selectivity. Finally, the β/α-selectivity during the glycosylation was enhanced to ≥99/1. The results obtained herein suggest that the protecting groups on the sugar connected to the 2-O of a glycosyl donor with axial-rich conformation can control the stereoselectivity of glycosylation.

  本文描述了先前报道的β/α-选择性为96/4的两个反例，使用乙基2-O-[2,3,4-三-O-叔丁基二甲基硅基(TBS)-α-L-鼠李糖吡喃糖苷]-3,4,6-三-O-TBS-硫代-β-D-葡萄糖吡喃糖苷作为糖基供体进行糖基化。此外，我们研究了胆固醇醇糖基化中鼠李糖部分保护基的影响，并揭示了β-选择性源于鼠李糖的3-O和4-O位置上的两个TBS基团。相比之下，鼠李糖2-O位置上的TBS基团阻碍了β-选择性。最终，糖基化过程中的β/α-选择性提高至≥99/1。本文获得的结果表明，与轴向富集构象的糖基供体的2-O相连的糖上的保护基可以控制糖基化的立体选择性。
• Synthesis of α-<scp>d</scp>-Glcp-(1→3)-α-<scp>d</scp>-Galf-(1→2)-α-<scp>l</scp>-Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-<scp>d</scp>-galactofuranosylation
  作者：Gabriel Gola、Carola Gallo-Rodriguez

  DOI：10.1039/c3ra45658g

  日期：——

  The synthesis of the trisaccharide α-D-Glcp-(1→3)-α-D-Galf-(1→2)-L-Rhap (3) constituent of Streptococcus pneumonia 22F was achieved with complete diastereoselectivity. This is the first example of a synthesis of an internal α-D-Galf containing oligosaccharide of a pathogen microorganism. Allyl α-D-galactofuranoside, used as novel precursor of the internal Galf, allowed the introduction of an orthogonal group at O-3. The trichloroacetimidate method was used for the construction of 1,2-cis-α-D-galactofuranosyl linkage. The influence of the 3-O-substituent (PMB, Bz, PFBz, PMBz, TIPS) was evaluated in benzylated galactofuranosyl trichloroacetimidate donors in terms of yield and selectivity of α-D-Galf-(1→2)-α-L-Rhap product as well as donor rearrangement by-product. Complete stereoselectivity was observed with all protecting groups used in the Galf donor, but the 3-O-benzoyl substitution gave the best yield. Protective groups were also evaluated in the rhamnoside acceptor, benzyl substitution was a requirement for complete stereoselectivity.

  以完全非对映选择性合成了肺炎链球菌 22F 的三糖δ±-D-Glcp-(1â3)-δ±-D-Galf-(1â2)-L-Rhap (3)。这是首次合成病原微生物内部含有δ-D-Galf 的寡糖。使用烯丙基δ±-D-半乳糖呋喃糖苷作为内部 Galf 的新型前体，可以在 O-3 处引入一个正交基团。三氯乙酰亚氨酸法用于构建 1,2-顺式-δ±-D-半乳糖呋喃糖基连接。根据δ-D-Galf-(1â2)-δ-L-Rhap 产物以及供体重排副产物的产量和选择性，评估了苄基半乳糖呋喃糖基三氯乙酰亚胺供体中 3-O 取代基（PMB、Bz、PFBz、PMBz、TIPS）的影响。在 Galf 供体中使用的所有保护基团都具有完全的立体选择性，但 3-O 苯甲酰基取代的产率最高。还对鼠李糖苷受体中的保护基团进行了评估，发现苄基取代是完全立体选择性的必要条件。
• A Versatile Strategy for the Synthesis of <i>N</i>-Acetyl-bacillosamine-Containing Disaccharide Building Blocks Related to Bacterial O-Antigens
  作者：Emiliano Bedini、Davide Esposito、Michelangelo Parrilli

  DOI：10.1055/s-2006-939057

  日期：——

  The synthetic path was then slightly modified to obtain a similar glycosyl donor with an axial acetyl group on position 4. This building block could be coupled to give a disaccharide, that after five steps (azido reduction, acetylation, O-deacetylation, mesylation, and azide substitution) afforded a bacillosamine-containing disaccharide with differently protected amino functions, in order to provide

  芽孢杆菌胺的 N-苯基三氟乙酰亚胺糖基供体，一种包含在来自病原菌的几种 0-抗原中的 2,4-二氨基糖，是从已知的全乙酰化 D-fucal 开始合成的，并被证明对与芽孢杆菌胺的高产偶联是有效的。含双糖。取决于溶剂和糖基受体，糖基化的立体选择性从中等到非常好。然后稍微修改合成路径以获得类似的糖基供体，在位置 4 上有一个轴向乙酰基。这个构建块可以偶联得到二糖，经过五个步骤（叠氮基还原、乙酰化、O-脱乙酰化、甲磺酰化和叠氮化物取代）提供了具有不同保护氨基功能的含杆胺二糖，
• Synthetic oligorhamnans related to the most common O-chain backbone from phytopathogenic bacteria
  作者：Emiliano Bedini、Antonella Carabellese、Daniela Comegna、Cristina De Castro、Michelangelo Parrilli

  DOI：10.1016/j.tet.2006.06.084

  日期：2006.9

  The synthesis of the tetrasaccharide rhamnanic motif alpha-L-Rha-(1 -> 3)-alpha-L-Rha-(1 -> 2)-alpha-L-Rha-(1 -> 2)-alpha-L-Rha and its dimerization to octasaccharide have been developed. Three different pathways toward the dimerization have been investigated; the best one was based on a [4+2]+2 stepwise condensation of a rhamnose tetrasaccharide with two rhamnosyl N-phenyl ttifluoroacetimidates as glycosyl donors and on an orthogonal set of protecting groups consisting of benzoyl, levulinoyl, and allyl groups. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of a hexasaccharide fragment of group E streptococci polysaccharide and the tetrasaccharide repeating unit of E. coli O7:K98:H6
  作者：Youlin Zeng、Fanzuo Kong

  DOI：10.1016/j.carres.2004.03.027

  日期：2004.6

  Syntheses of a hexasaccharide, the dimer of the repeating unit of the group E streptococci polysaccharide, and a tetrasaccharide, the repeating unit of the E. coli 07:K98:H6, were achieved by constructing alternate alpha-L-(l --> 2)- and alpha-L-(1 --> 3)linked L-rhamnopyranose backbones and substituting with beta-linked D-glucopyranose side chains for the former, and a D-gluco-pyranosyluronate branch for the latter, respectively, at O-2 of the L-rhamnose ring. (C) 2004 Elsevier Ltd. All rights reserved.Syntheses of a hexasaccharide, the dimer of the repeating unit of the group E streptococci polysaccharide, and a tetrasaccharide, the repeating unit of the E. coli O7:K98:H6, were achieved by constructing alternate alpha-L-(1 --> 2)- and alpha-L-(1 --> 3)-linked L-rhamnopyranose backbones and substituting with P-linked D-glucopyranose side chains for the former, and a D-gluco-pyranosyluronate branch for the latter, respectively, at O-2 of the L-rhamnose ring. (C) 2004 Elsevier Ltd. All rights reserved.