2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-1,2-O-isopropylidene-α-D-glucofuranose | 331969-91-6

• 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: 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-1,2-O-isopropylidene-α-D-glucofuranose
• 英文别名: [(2R,3R,4S,5R,6S)-6-[[(3aR,5R,6S,6aR)-5-[(1R)-1,2-dihydroxyethyl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 331969-91-6
• 化学式: C₄₃H₄₂O₁₅
• 分子量: 798.797
• InChiKey: QWVYDHIZDLIHCV-YGRZXJGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  58
• 可旋转键数：
  17
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  192
• 氢给体数：
  2
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-1,2-O-isopropylidene-α-D-glucofuranose 在 三氟甲磺酸三甲基硅酯 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 23.0h， 生成 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-[2,3,4-tri-O-benzoyl-β-D-glucopyranosyl-(1->6)]-1,2-O-isopropylidene-α-D-glucopyranose
  参考文献：
  名称：

  Phytoalexin-Elicitor Active β-(1→3)-Branched β-(1→6)-连接七葡萄糖及其十二烷基糖苷的高效合成

  摘要：

  采用 1,2:5,6-二-O-异亚丙基-α-D-呋喃葡萄糖、2,3,4,6-四O-苯甲酰基-α-D-吡喃葡萄糖基三氯乙酰亚胺酯和6-O-乙酰基-2,3,4-三-O-苯甲酰基-α-D-吡喃葡萄糖基三氯乙酰亚胺酯通过区域选择性和立体选择性方式进行。使用开发的策略制备了具有植物抗毒素诱导剂活性的β-(1→3)-支链β-(1→6)-连接的七葡萄糖1及其十二烷基糖苷2。生物测定表明，十二烷基 β-(1→3)-支链 β-(1→6)-连接的六葡萄糖苷 2 的植物抗毒素诱导剂活性略高于相应的还原端游离七葡萄糖 1。

  DOI：

  10.1055/s-2003-37644
• 作为产物：
  描述：

  1,2,3,4,6-戊-O-苯甲酰基-D-吡喃葡萄糖苷 在 三氟甲磺酸三甲基硅酯 、 氨 、 potassium carbonate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 59.0h， 生成 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl-(1->3)-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Phytoalexin-Elicitor Active β-(1→3)-Branched β-(1→6)-连接七葡萄糖及其十二烷基糖苷的高效合成

  摘要：

  采用 1,2:5,6-二-O-异亚丙基-α-D-呋喃葡萄糖、2,3,4,6-四O-苯甲酰基-α-D-吡喃葡萄糖基三氯乙酰亚胺酯和6-O-乙酰基-2,3,4-三-O-苯甲酰基-α-D-吡喃葡萄糖基三氯乙酰亚胺酯通过区域选择性和立体选择性方式进行。使用开发的策略制备了具有植物抗毒素诱导剂活性的β-(1→3)-支链β-(1→6)-连接的七葡萄糖1及其十二烷基糖苷2。生物测定表明，十二烷基 β-(1→3)-支链 β-(1→6)-连接的六葡萄糖苷 2 的植物抗毒素诱导剂活性略高于相应的还原端游离七葡萄糖 1。

  DOI：

  10.1055/s-2003-37644

文献信息

• A general strategy for the synthesis of 3,6-branched gluco-oligosaccharides: facile synthesis of the phytoalexin elicitor oligosaccharides
  作者：Jun Ning、Yuetao Yi、Fanzuo Kong

  DOI：10.1016/s0040-4039(02)01143-7

  日期：2002.8

  A general method for the synthesis of 3,6-branched gluco-oligosaccharides has been developed. As a typical example of the method, the synthesis of the glucohexatose phytoalexin elicitor on a large scale was achieved via coupling of a trisaccharide donor with a trisaccharide acceptor. The donor and acceptor were prepared easily from 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, 2,3,4,6-tetra-O-ben

  已经开发了合成3，6-支链葡萄糖寡糖的通用方法。作为该方法的典型实例，通过三糖供体与三糖受体的偶联来大规模合成葡萄糖己糖植物抗毒素。供体和受体可以容易地由1,2：5,6-二-O-异亚丙基-α-d-呋喃呋喃糖，2,3,4,6-四-O-苯甲酰基-α-d-吡喃葡萄糖基三氯乙酰亚胺酸酯和以区域和立体选择性的方式，6 - O-乙酰基-2,3,4-三-O-苯甲酰基-α-d-吡喃葡萄糖基三氯乙酰亚胺酸酯。通过该策略也已经容易地合成了引发剂的高级寡糖，包括七，九，九，十二和十四糖。
• Synthesis of two isomeric pentasaccharides, the possible repeating unit of the β-glucan from the micro fungus Epicoccum nigrum Ehrenb. ex Schlecht
  作者：Ying Zeng、Wenhui Zhang、Jun Ning、Fanzuo Kong

  DOI：10.1016/s0008-6215(02)00317-8

  日期：2002.11

  ta-D-Glcp-(1-->3)-beta-D-Glcp-(1-->6)]-beta-D-Glcp (II), the possible repeating unit of the beta-glucan from the micro fungus Epicoccum nigrum Ehrenb. ex Schlecht, were synthesized as their 4-methoxyphenyl glycosides in a regio- and stereoselective manner. The pentasaccharide I was obtained from 3-O-selective glycosylation of 4-methoxyphenyl 4,6-O-benzylidene-beta-D-glucopyranoside (12) with 2,3,4

  两个同分异构的五糖β-D-Glcp-（1-> 3）-[β-D-Glcp-（1-> 6）]-beta-D-Glcp-（1-> 3）-[beta -D-Glcp-（1-> 6）]-beta-D-Glcp（I）和beta-D-Glcp-（1-> 6）-beta-D-Glcp-（1-> 3） -[β-D-Glcp-（1-> 3）-β-D-Glcp-（1-> 6）]-β-D-Glcp（II），可能是来自微型真菌Epicoccum nigrum Ehrenb。如Schlecht，以区域和立体选择性的方式合成它们的4-甲氧基苯基糖苷。由4-甲氧基苯基4,6-O-亚苄基-β-D-吡喃葡萄糖苷（12）与2,3,4,6-四-O-苯甲酰基-β-D的3-O-选择性糖基化反应获得五糖I -吡喃葡萄糖基-（1-> 3）-[2,3,4,6-四-O-苯甲酰基-β-D-吡喃葡萄糖基-（1-> 6）]-2,4-二-O-乙酰基
• Synthesis of β-(1→6)-branched β-(1→3) glucohexaose and its analogues containing an α-(1→3) linked bond with antitumor activity
  作者：Jun Ning、Wenhui Zhang、Yuetao Yi、Guangbin Yang、Zhikui Wu、Jie Yi、Fanzuo Kong

  DOI：10.1016/s0968-0896(03)00118-4

  日期：2003.5

  A beta-(1 --> 6)-branched beta-(1 --> 3)-glucohexaose, present in many biologically active polysaccharides from traditionally herbal medicines such as Ganoderma lucidum, Schizophyllum commune and Lentinus edodes, was synthesized as its lauryl glycoside 32, and its analogues 18, 20 and 33 containing an alpha-(l --> 3) linked bond were synthesized. It is interesting to find that coupling of a 3,6-branched acylated trisaccharide trichloroacetimidate donor 9 with 3,6-branched acceptors 13 and 16 with 3'-OH gave the alpha-(1 --> 3)linked hexasaccharides 17 and 19, respectively, in spite of the presence of C-2 ester capable of neighboring group participation. However, coupling of 9 with 4-methoxyphenyl 4,6-0-benzylidene-beta-D-glucopyranoside (27) selectively gave beta-(1 --> 3)-linked tetrasaccharide 28. Simple chemical transformation of the tetrasaccharide 28 gave acylated tetrasaccharide trichloroacetimidate 29. Coupling of 29 with lauryl (I --> 6)-linked disaccharide 26 with 3-OH gave beta-(I --> 3)-linked hexasaccharide 30 as the major product. Bioassay showed that in combination with the chemotherapeutic agent cyclophospamide (CPA), the hexaose 18 at a dose of 0.5-1 mg/kg substantially increased the inhibition of S 180 for CPA, but decreased the toxicity caused by CPA. Some of these oligosaccharides also inhibited U-14 noumenal tumor in mice effectively. (C) 2003 Elsevier Science Ltd. All rights reserved.
• EP1405855
  申请人：——

  公开号：——

  公开（公告）日：——
• Large-Scale Preparation of the Phytoalexin Elicitor Glucohexatose and Its Application as a Green Pesticide
  作者：Jun Ning、Fanzuo Kong、Bangmao Lin、Huide Lei

  DOI：10.1021/jf020683x

  日期：2003.2.1

  Large-scale preparation of the phytoalexin elicitor was achieved through a highly regio- and sterereoselective synthesis using 2,3,4,6-tetra-O-benzoyl-D-glucopyranosyl trichloroacetimidate (1), 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (2), and 6-O-acetyl-2,3,4-tri-O-benzoyl-alpha-D-glucopyranosyl trichloroacetimidate (3) as the synthons. Coupling of 1 with 2 gave the 1-->3-linked disaccharide; subsequent selective removal of 5,6-O-isopropylidene to give 5 followed by selective 6-O-glycosylation with 1 afforded the trisaccharide 6. Hydrolysis to remove the 1,2-O-isopropylidene was accompanied by ring expansion, giving 3,6-branched pyranosyl trisaccharide. Acetylation, selective 1-O-deacetylation, and activation with trichloroacetonitrile gave the trisaccharide donor 7. The trisaccharide acceptor 9 was prepared from condensation of the disaccharide 5 with 3 and subsequent 6-O-deacetylation. Coupling of the trisaccharide donor 7 with the trisaccharide acceptor 9 and subsequent deprotection afforded the glucohexatose elicitor. The cost of the produced glucohexatose should be low enough to allow its applications in agriculture as a green pesticide. At a concentration of 5-10 mg/L, the resultant elicitor was used to treat growing orange trees and harvested oranges, giving very encouraging results, comparable with those obtained using commercial pesticides at a concentration of 1400 mg/L (Topsin-M) for growing trees and 900 mg/L (Tecto) for harvested oranges, respectively. Treatment of tomato leaves against Botrytis cinerea with the synthetic elicitor at a concentration of 10 mg/L gave 82% inhibition, comparable with the inhibition of 84% by Wanmeiling at a concentration of 1000 mg/L. Treatment of tea leaves also showed promising results.