methyl 2,4,6-tri-O-benzoyl-β-D-glucopyranoside | 86394-88-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4,6-tri-O-benzoyl-β-D-glucopyranoside
• 英文别名: Methyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosid；[(2R,3S,4S,5R,6R)-3,5-dibenzoyloxy-4-hydroxy-6-methoxyoxan-2-yl]methyl benzoate
• CAS: 86394-88-9
• 化学式: C₂₈H₂₆O₉
• 分子量: 506.509
• InChiKey: FAZUIGXOWOIOEH-STSWTCBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  37.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  117.59
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  methyl 2,4,6-tri-O-benzoyl-β-D-glucopyranoside 在 palladium on activated charcoal sodium hydroxide 、 三氟甲磺酸三甲基硅酯 、 1,1-二氯甲醚 、 3 A molecular sieve 、 氢气 、 sodium methylate 、 silver trifluoromethanesulfonate 、 zinc(II) chloride 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 53.25h， 生成 5-aminopentyl O-<4,6-O((S)-1-carboxyethylidene)-3-O-methyl-β-D-glucopyranosyl>-(1<*>3)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthetic studies toward pyruvate acetal containing saccharides. Synthesis of the carbohydrate part of the Mycobacterium smegmatis pentasaccharide glycolipid and fragments thereof for the preparation of neoantigens

  摘要：

  A series of 2,3-di-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-D-glucopyranosyl donors (beta-phenylthio 3, bromide 4, alpha-chloride 5, beta-fluoride 6, and trichloroacetimidate 7) were prepared from the corresponding alpha-allyl glucoside 1 via the deallylated glucose 2 and were tested in glycosylation reactions with methanol to give the pyruvylated methyl glucosides 8 and 9 and with methyl 2,4,6-tri-O-benzoyl-beta-D-glucopyranoside 10 to give the disaccharide 11. Best results with respect to yield and beta-selectivity of the coupling were achieved with imidate 7. Thus, the 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-3-O-methyl-D-glucopyranosyl trichloroacetimidate 14 was prepared from its benzyl glucoside 12 and used for the synthesis of fragments related to the Mycobacterium smegmatis lipopentasaccharide. Trimethylsilyl trifluoromethanesulfonate-mediated condensation of 14, 5-[(benzyloxycarbonyl)amino]pentanol, and 10, respectively, followed by deblocking of the products 15 and 17 gave the pyruvylated aminopentyl glucoside 16 and methyl laminaribioside 18. Treatment of 17 with dichloromethyl methyl ether gave the laminaribiosyl chloride 19, coupling of which with protected 5-aminopentanol gave 20 also obtained from 14 and the monosaccharide nucleophile 26. The trisaccharide 5-aminopentyl glycoside fragment 42 was prepared by first coupling of 14 and benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside 30 that was converted to the bispyruvylated laminaribiose imidate 33, followed by condensation with thioglycoside 38 obtainable in four steps from 1,2,4,6-tetra-O-acetyl-3-O-benzyl-beta-D-glucopyranose to give the trisaccharide ethyl thioglycoside 40. Next, NIS-mediated condensation of 40 and 5-[(benzyloxycarbonyl)amino]pentanol followed by deblocking gave 42. Pentasaccharide 45 was similarly prepared from 40 and hepta-O-benzoyltrehalose 43 to give first the blocked saccharide 44, deblocking of which afforded the target pentasaccharide.

  DOI：

  10.1021/jo00057a021

文献信息

• A combined nuclear magnetic resonance and molecular dynamics study of the two structural motifs for mixed-linkage β-glucans: methyl β-cellobioside and methyl β-laminarabioside
  作者：Niels Johan Christensen、Peter Ibsen Hansen、Flemming Hofmann Larsen、Tore Folkerman、Mohammed Saddik Motawia、Søren Balling Engelsen

  DOI：10.1016/j.carres.2009.12.009

  日期：2010.2

  beta-laminarabioside were investigated by NMR spectroscopy and explicit solvation molecular dynamics simulations using the carbohydrate solution force field (CSFF). Adiabatic maps produced with this force field displayed 4 minima A: (Phi=300 degrees , Psi=280 degrees), B: (Phi=280 degrees , Psi=210 degrees), C: (Phi=260 degrees , Psi=60 degrees), and D: (Phi=60 degrees , Psi=260 degrees) for methyl beta-cellobioside

  两种双糖甲基β-纤维二糖苷和甲基β-laminarabioside的构象和水合特性通过NMR光谱和使用碳水化合物溶液力场（CSFF）的显式溶剂化分子动力学模拟进行了研究。用此力场生成的绝热图显示4个极小值：A：（Phi = 300度，Psi = 280度），B：（Phi = 280度，Psi = 210度），C：（Phi = 260度，Psi = 60度） ）和D：甲基β-纤维二糖苷的（Phi = 60度，Psi = 260度）和3个极小值A：（Phi = 290度，Psi = 130度），B：（Phi = 270度，Psi = 290度） ），C ：(甲基β-laminarabioside的（Phi = 60度，Psi = 120度）。分子动力学模拟是从所有最小值开始的。对于每种二糖，模拟从A最小值开始进行了50ns，而另一个最小值被探索了10ns。模拟显示两种化合物的两个稳定最小值。对
• Ziegler, Thomas; Eckhardt, Elisabeth; Herold, Gerhard, Liebigs Annalen der Chemie, 1992, # 5, p. 441 - 452
  作者：Ziegler, Thomas、Eckhardt, Elisabeth、Herold, Gerhard

  DOI：——

  日期：——
• α-Fucosylation by 2,3,4-tri-O-benzoyl-α-l-fucopyranosyl bromide under Helferich conditions
  作者：Nikolay E. Nifant'ev、Vera Y. Amochaeva、Alexander S. Shashkov、Nikolay K. Kochetkov

  DOI：10.1016/0008-6215(93)80023-8

  日期：1993.4

  Glycosylation of various carbohydrate mono- and di-hydroxy derivatives with 2,3,4-tri-O-benzoyl-alpha-L-fucopyranosyl bromide under Helferich conditions is stereoselective for acceptors that contain an axial hydroxyl group and/or neighbouring acyloxy, phthalimido, or bulky monosaccharide substituents.