methyl (allyl 2,3-di-O-benzyl-β-D-galactopyranosid)uronate | 113765-22-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (allyl 2,3-di-O-benzyl-β-D-galactopyranosid)uronate
• 英文别名: methyl (2S,3R,4S,5R,6R)-3-hydroxy-4,5-bis(phenylmethoxy)-6-prop-2-enoxyoxane-2-carboxylate
• CAS: 113765-22-3
• 化学式: C₂₄H₂₈O₇
• 分子量: 428.482
• InChiKey: KYILKXXKHMRNRE-KQWJERSKSA-N

物化性质

• 熔点：
  111 °C
• 沸点：
  553.3±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (allyl 2,3-di-O-benzyl-β-D-galactopyranosid)uronate 在 吡啶 、 iodonium(di-γ-collidine) perchlorate 、 水 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 31.67h， 生成 methyl (methyl 4-O-acetyl-2,3-di-O-benzyl-α-D-galactopyranosyluronate)-(1->4)-(allyl 2,3-di-O-benzyl-β-D-galactopyranosid)uronate
  参考文献：
  名称：

  Synthesis of Homogalacturonan Fragments

  摘要：

  Glycosylation of the D-galacturonic acid ester derivatives 15 and 17, which are prepared directly from D-galacturonic acid, with the thioglycosides 28 and 32, derived from the same sugar, provides alpha(1-->4)-linked dimers. The formation of the glycosidic linkage between the galacturonic acid moieties is best achieved by iodonium di-sym-collidine perchlorate promotion. Thus, the 4'-O-p-methoxybenzyl dimer 38 can be obtained in 64% yield. Partial deprotection of the 4'-O-position provided the glycosyl acceptor 36, which was coupled with the donor 32 to yield the alpha(1 "-->4')-linked trimer 39 (48%). Approximately 8% of the beta(1 "-->4')-coupled isomer was observed in the C-13 NMR spectrum of the reaction mixture.

  DOI：

  10.1080/07328300008544125
• 作为产物：
  描述：

  allyl β-D-galactopyranoside 在 platinum(IV) oxide 、 苯磺酸 氧气 、 sodium hydride 、 碳酸氢钠 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 吡啶 、 甲醇 、 乙醚 、 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.5h， 生成 methyl (allyl 2,3-di-O-benzyl-β-D-galactopyranosid)uronate
  参考文献：
  名称：

  Synthesis of methyl (allyl 2,3-di-O-benzyl-β-d-galactopyranosid)uronate and methyl (2,3-di-O-benzyl-α- and β-d-galactopyranosyl fluoride)uronate

  摘要：

  DOI：

  10.1016/s0008-6215(00)90828-0

文献信息

• Efficient synthesis of building blocks for branched rhamnogalacturonan I fragments
  作者：Amayak Pogosyan、Andreas Gottwald、Dirk Michalik、Hans-Ulrich Endress、Christian Vogel

  DOI：10.1016/j.carres.2013.06.019

  日期：2013.10

  syl)-(1→4)-2-O-acetyl-3-O-benzyl-α-l-rhamnopyranoside (5) was synthesized under Helferich conditions. Module 5 was converted to 2,3,4,6-tetra-O-benzoyl-β-d-galactopyranosyl-(1→4)-2-O-acetyl-3-O-benzyl-α-l-rhamnopyranosyl bromide (8) which was then coupled with methyl (allyl 2,3-di-O-benzyl-β-d-galactopyranosid)uronate (11) to provide methyl (2,3,4,6-tetra-O-benzoyl-β-d-galactopyranosyl)-(1→4)-(2-O

  从烯丙基2-O-乙酰基-3-O-苄基-α-1-鼠李糖吡喃糖苷（3）开始，烯丙基（2,3,4,6-四-O-苯甲酰基-β-d-吡喃并吡喃糖基）-（1→在Helferich条件下合成了4）-2-O-乙酰基-3-O-苄基-α-1-鼠李吡喃糖苷（5）。将模块5转化为2,3,4,6-四-O-苯甲酰基-β-d-吡喃半乳糖基-（1→4）-2-O-乙酰基-3-O-苄基-α-1-鼠李糖基吡喃糖基溴化物（然后将其与（8,3-烯丙基2,3-二-O-苄基-β-d-吡喃半乳糖苷）尿酸酯（11）偶联以提供甲基（2,3,4,6-四-O-苯甲酰基-β- d-半乳糖吡喃糖基）-（1→4）-（2-O-乙酰基-3-O-苄基-α-1-鼠李糖基吡喃糖基）-（1→4）-（烯丙基2,3-二-O-苄基-β -d-吡喃半乳糖苷）尿酸盐（14）。或者，将模块5转化成适合作为烯丙基的2,3,4,6-四-O-苯甲酰基-β-d-吡喃半乳糖基-（1→
• 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。
• A highly efficient, practical, and stereoselective approach to the synthesis of α 1→4 linked galactooligosaccharides
  作者：Yoshiaki Nakahara、Tomoya Ogawa

  DOI：10.1016/s0040-4039(00)96193-8

  日期：1987.1

  Exclusive formation of α1→4 linked galactopyranosyl oligosaccharides could be achieved by employing glycosyl fluorides. The observed diastereofacial selectivity was explained in terms of the nucleophilic attack of glycosyl acceptors toward convex face of the glycosyl fluorides.

  通过使用糖基氟化物可以实现α1→4连接的吡喃半乳糖基寡糖的排他性形成。用糖基受体向糖基氟化物的凸面的亲核攻击来解释观察到的非对面选择性。
• Synthesis of oligosaccharide fragments of the rhamnogalacturonan of Nerium indicum
  作者：Yuyong Ma、Xin Cao、Biao Yu

  DOI：10.1016/j.carres.2013.05.008

  日期：2013.8

  Three trisaccharides, one pentasaccharide, and one heptasaccharide, namely alpha-D-GalA-(1 -> 2)-alpha-L-Rha(1 -> 4)-beta-D-GalA-OC3H7 (1), alpha-L-Rha-(1 -> 4)-alpha-D-GalA-(1 -> 4)-beta-D-GalA-OC3H7 (2), alpha-D-GalA-(1 -> 4)-alpha-D-GalA-(1 -> 2)-alpha-L-Rha-OC3H7 (3), alpha-D-GalA-(1 -> 2)-alpha-L-Rha-(1 -> 4)-alpha-D-GalA-(1 -> 2)-alpha-L-Rha-(1 -> 4)-beta-D-GalA-OC3H7 (4), and alpha-D-GalA-(1 -> 2)-alpha-L-Rha-(1 -> 4)-alpha-D-GalA-(1 -> 2)-alpha-L-Rha-(1 -> 4)-alpha-D-GalA-(1 -> 2)-alpha-L-Rha-(1 -> 4)-beta-D-GalA-OC3H7 (5), which are relevant to the fragments of the rhamnogalacturonan of Nerium indicum, were concisely synthesized. The syntheses feature highly stereoselective formation of the alpha-D-GalA-linkage with GalA N-phenyltrifluoroacetimidates as donors. (c) 2013 Elsevier Ltd. All rights reserved.
• 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.