methyl 2,3-O-methylorthoacetyl α-L-rhamnopyranoside | 406460-49-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-O-methylorthoacetyl α-L-rhamnopyranoside
• 英文别名: methyl 2,3-O-methylorthoacetyl-α-L-rhamnopyranoside；(3aR,4R,6S,7S,7aR)-2-ethoxy-4-methoxy-2,6-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 406460-49-9
• 化学式: C₁₁H₂₀O₆
• 分子量: 248.276
• InChiKey: XDAFFJWWMHHSLO-RYKMKORYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-O-methylorthoacetyl α-L-rhamnopyranoside 在 吡啶 、 三氟甲磺酸 、 硫酸 、 三氟化硼乙醚 、 溶剂黄146 作用下， 以 正庚烷 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 methyl 2-O-acetyl-4-O-benzoyl-3-O-benzyl-1-thio-α-L-rhamnopyranoside
  参考文献：
  名称：

  BLOCK SYNTHESIS WITH GALACTURONATE TRICHLOROACETIMIDATES1

  摘要：

  The disaccharide methyl (4-O-benzoyl-3-O-benzyl-2-O-acetyl-alpha -L-rhamno pyranosyl)-(1 -->4)-(allyl 2,3-di-O-benzyl-beta -D-galactopyranosid)uronate (13) was obtained in an excellent yield of 88% using methyl (allyl 2,3-di-O-benzyl-beta -D-galactopyranosid)uronate (12) as the glycosyl acceptor and a slight excess Of the 1,2-di-O-acetyl-rhamnoglycosyl donor 5a. Disaccharide 13 is a key intermediate that can be used either as a glycosyl acceptor or glycosyl donor for the preparation of rhamnogalacturonan fragments. Here, introduction of the trichloroacetimidate function at the anomeric center gave the disaccharide glycosyl donor 28, which could be applied in a blockwise glycosylation reaction to form the L-Rha-alpha (1 -->4)-D-GalA-alpha (1 -->4)-D-GalA trisaccharide 29. Generally, on condition that no neighboring group effect influenced the reaction at the anomeric center of the alpha -trichloroacetimidate galacturonate glycosyl donors (20-22,28), alpha -glycosidic linkages were nearly exclusively formed, except in the case of the 4-O-methylgalactopyranosyluronate 22.

  DOI：

  10.1081/car-100108276
• 作为产物：
  描述：

  L-rhamnopyranose 在 Dowex-H⁽¹⁺⁾ 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 2,3-O-methylorthoacetyl α-L-rhamnopyranoside
  参考文献：
  名称：

  Total synthesis of (+)-asperlin

  摘要：

  DOI：

  10.1016/s0957-4166(00)82363-0

文献信息

• A simple one-pot method for the synthesis of partially protected mono- and disaccharide building blocks using an orthoesterification–benzylation–orthoester rearrangement approach
  作者：Balaram Mukhopadhyay、Robert A Field

  DOI：10.1016/s0008-6215(03)00349-5

  日期：2003.9

  A simple one-pot method is reported for making partially protected glycosyl acceptors from O-methyl or S-alkyl/aryl glycosides of D-glucose, D-galactose, D-arabinose, L-rhamnose, L-fucose and lactose via orthoester formation, benzylation and selective hydrolysis.

  报道了一种简单的一锅法，其通过原酸酯形成由D-葡萄糖，D-半乳糖，D-阿拉伯糖，L-鼠李糖，L-岩藻糖和乳糖的O-甲基或S-烷基/芳基糖苷制备部分受保护的糖基受体。 ，苄基化和选择性水解。
• Synthesis of a 2,3,4-Triglycosylated Rhamnoside Fragment of Rhamnogalacturonan-II Side Chain A Using a Late Stage Oxidation Approach
  作者：Anne-Laure Chauvin、Sergey A. Nepogodiev、Robert A. Field

  DOI：10.1021/jo0482864

  日期：2005.2.1

  RG-II, a key component of plant primary cell walls, is known to exist as a dimer formed by means of borate diester cross-links between apiosyl residues of one of its constituent side-chain oligosaccharides. Described herein is the strategy for the synthesis of the branched tetrasaccharide α-d-GalA-(1→2)-[β-d-GalA-(1→3)]-[α-l-Fuc-(1→4)]-α-l-Rha-OMe, an RG-II fragment that is linked to the apiosyl residue

  果胶多糖 RG-II 是植物初生细胞壁的关键成分，已知以二聚体的形式存在，该二聚体是通过其组成侧链寡糖之一的仙人掌残基之间的硼酸二酯交联形成的。本文描述的是合成支链四糖α - d -GalA-(1→2)-[β- d - GalA-(1→3)]-[α -1- Fuc-(1→4)的策略] -α- l -Rha-OMe，一种 RG-II 片段，与被认为是 RG-II 二聚体中硼酸盐络合的原因的 apiosyl 残基相连。源自 4 - O-甲氧基苄基-α- d甲酯的关键 2,3-原乙酸酯的鼠李糖苷受体的迭代糖基化-吡喃鼠李糖苷提供受保护的四糖。随后通过去除保护基团随后通过TEMPO介导的将吡喃半乳糖基残基氧化为吡喃半乳糖醛酸来制备目标二羧酸糖。
• Total Synthesis of Jadomycins B, S, T, and ILEVS1080
  作者：Xiaoyu Yang、Biao Yu

  DOI：10.1002/chem.201301297

  日期：2013.6.24

  Sweetening up jadomycin A: The first total synthesis of jadomycins B, S, T, and ILEVS1080 has been achieved, featuring construction of the unique 8H‐benz[b]oxazolo[3,3‐f]phenanthridine skeleton by biomimetic condensation of a quinone aldehyde with amino acid sodium salts and elaboration of the glycosides by Mitsunobu condensation (see figure).

  增甜杰霉素霉素：杰霉素霉素B，S，T和ILEVS1080的第一个全合成物已经实现，其特征是通过仿生缩合a来构建独特的8 H-苯并[ b ]恶唑并[3,3-f]菲啶骨架。醌醛与氨基酸钠盐的结合，以及通过Mitsunobu缩合精制糖苷（见图）。
• Synthesis of rhamnogalacturonan I fragments by a modular design principle
  作者：Navid Nemati、Gnuni Karapetyan、Birte Nolting、Hans-Ulrich Endress、Christian Vogel

  DOI：10.1016/j.carres.2008.03.020

  日期：2008.7

  improved syntheses of methyl 2-O-acetyl-3-O-benzyl-alpha-L-rhamnopyranoside (12) and 1,2-di-O-acetyl-3-O-benzyl-alpha-L-rhamnopyranose (15), which were used as glycosyl acceptor and donor, respectively, are described. Glycosylation of the O-4 position of both rhamnose derivatives with 2,3,4,6-tetra-O-benzoyl-alpha-D-galactopyranosyl bromide (26) provided disaccharides 27 and 29. After partial deprotection

  改进的甲基2-O-乙酰基-3-O-苄基-α-L-鼠李吡喃糖苷（12）和1,2-二-O-乙酰基-3-O-苄基-α-L-鼠李糖吡喃糖（15）的合成分别描述了分别用作糖基受体和供体的糖苷。两种鼠李糖衍生物的O-4位置被2,3,4,6-四-O-苯甲酰基-α-D-吡喃半乳糖基溴化物糖基化（26），得到二糖27和29。在27的部分脱保护并偶联后，用二糖19得到28，得到四糖31。此外，将29转化为相应的溴化物30并与半乳糖醛酸酯16和32偶联分别提供了三糖33和34，其可以被认为是分支的鼠李糖半乳糖醛酸聚糖片段的结构单元。
• BLOCK SYNTHESIS WITH GALACTURONATE TRICHLOROACETIMIDATES1
  作者：Birte Nolting、Hanna Boye、Christian Vogel

  DOI：10.1081/car-100108276

  日期：——

  The disaccharide methyl (4-O-benzoyl-3-O-benzyl-2-O-acetyl-alpha -L-rhamno pyranosyl)-(1 -->4)-(allyl 2,3-di-O-benzyl-beta -D-galactopyranosid)uronate (13) was obtained in an excellent yield of 88% using methyl (allyl 2,3-di-O-benzyl-beta -D-galactopyranosid)uronate (12) as the glycosyl acceptor and a slight excess Of the 1,2-di-O-acetyl-rhamnoglycosyl donor 5a. Disaccharide 13 is a key intermediate that can be used either as a glycosyl acceptor or glycosyl donor for the preparation of rhamnogalacturonan fragments. Here, introduction of the trichloroacetimidate function at the anomeric center gave the disaccharide glycosyl donor 28, which could be applied in a blockwise glycosylation reaction to form the L-Rha-alpha (1 -->4)-D-GalA-alpha (1 -->4)-D-GalA trisaccharide 29. Generally, on condition that no neighboring group effect influenced the reaction at the anomeric center of the alpha -trichloroacetimidate galacturonate glycosyl donors (20-22,28), alpha -glycosidic linkages were nearly exclusively formed, except in the case of the 4-O-methylgalactopyranosyluronate 22.