diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorohthalimido)-β-D-glucopyranoside | 308320-83-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorohthalimido)-β-D-glucopyranoside
• 英文别名: diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorophthalimido)-β-D-glucospyranoside；diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorophthalimido)-β-D-glucopyranoside；diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-β-D-glucopyranoside；[(2R,3S,4R,5R,6R)-3,4-diacetyloxy-5-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)-6-[(1S,2S,4S,5'R,6R,7S,8R,9S,12S,13R,16S)-5',7,9,13-tetramethylspiro[5-oxapentacyclo[10.8.0.02,9.04,8.013,18]icos-18-ene-6,2'-oxane]-16-yl]oxyoxan-2-yl]methyl acetate
• CAS: 308320-83-4
• 化学式: C₄₇H₅₇Cl₄NO₁₂
• 分子量: 969.781
• InChiKey: XKXZYBVNMBTERU-ZOIRIMMQSA-N

物化性质

• 熔点：
  257-258 °C
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  64
• 可旋转键数：
  10
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  153
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorohthalimido)-β-D-glucopyranoside 在 一水合肼 、 三乙胺 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 24.0h， 生成 diosgenyl 2-acetamido-2-deoxy-β-D-glucospyranoside
  参考文献：
  名称：

  Synthesis and induction of apoptosis in B cell chronic leukemia by diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride and its derivatives

  摘要：

  2-Acetamido-2-deoxy-D-glucose hydrochloride (D-glucosamine hydrochloride) has been used for the preparation of 1,3.4.6-tetra- O-acetyl-2-deoxy-2-trifluoroacetqamido-beta- (4) and 2-tetrachlorophthalimido-alpha, beta-D-glucopyranose (6) which have been transformed into the appropriate bromides and the chloride. Both bromo and chloro sugars were used as a glycosyl donors for the glycosylation of diosgenin [(25R)-spirost-5-en-3beta-ol]. These condensations were conducted under mild conditions, using silver triflate as a promoter, and gave diosgenyl glycosides 9 and 12. Each of them was converted into diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride (11) and N-acylamido derivatives. The structures of all new glycosides were established by H-1 and C-13 NMR spectroscopy. These diosgenyl glycosides are the first saponins containing the D-glucosamine residue that have been synthesized. These compounds show promising antitumor activities, The synthetic saponins increase the number of apoptotic B cells, in combination with cladribine (2-CdA). that are isolated from chronic lymphotic leukemia (B-CLL) patients. (C) 2002 Published by Elsevier Science Lid.

  DOI：

  10.1016/s0008-6215(02)00407-x
• 作为产物：
  描述：

  四氯苯二甲酸酐 在 吡啶 、 氢溴酸 、 sodium methylate 、 silver trifluoromethanesulfonate 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 25.0h， 生成 diosgenyl 3,4,6-tri-O-acetyl-2-deoxy-2-(3,4,5,6-tetrachlorohthalimido)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis and induction of apoptosis in B cell chronic leukemia by diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride and its derivatives

  摘要：

  2-Acetamido-2-deoxy-D-glucose hydrochloride (D-glucosamine hydrochloride) has been used for the preparation of 1,3.4.6-tetra- O-acetyl-2-deoxy-2-trifluoroacetqamido-beta- (4) and 2-tetrachlorophthalimido-alpha, beta-D-glucopyranose (6) which have been transformed into the appropriate bromides and the chloride. Both bromo and chloro sugars were used as a glycosyl donors for the glycosylation of diosgenin [(25R)-spirost-5-en-3beta-ol]. These condensations were conducted under mild conditions, using silver triflate as a promoter, and gave diosgenyl glycosides 9 and 12. Each of them was converted into diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride (11) and N-acylamido derivatives. The structures of all new glycosides were established by H-1 and C-13 NMR spectroscopy. These diosgenyl glycosides are the first saponins containing the D-glucosamine residue that have been synthesized. These compounds show promising antitumor activities, The synthetic saponins increase the number of apoptotic B cells, in combination with cladribine (2-CdA). that are isolated from chronic lymphotic leukemia (B-CLL) patients. (C) 2002 Published by Elsevier Science Lid.

  DOI：

  10.1016/s0008-6215(02)00407-x

文献信息

• <i>N</i>-Alkyl derivatives of diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside; synthesis and antimicrobial activity
  作者：Agata Walczewska、Daria Grzywacz、Dorota Bednarczyk、Małgorzata Dawgul、Andrzej Nowacki、Wojciech Kamysz、Beata Liberek、Henryk Myszka

  DOI：10.3762/bjoc.11.97

  日期：——

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside is a synthetic saponin exhibiting attractive pharmacological properties. Different pathways tested by us to obtain this glycoside are summarized here. Moreover, the synthesis of N-alkyl and N,N-dialkyl derivatives of the glucopyranoside is presented. Evaluation of antibacterial and antifungal activities of these derivatives indicates that they have no inhibitory activity against Gram-negative bacteria, whereas many of the tested N-alkyl saponins were found to inhibit the growth of Gram-positive bacteria and human pathogenic fungi.

  Diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside是一种具有吸引人的药理特性的合成皂苷。我们测试了不同的途径来获得这种糖苷，这里总结了这些途径。此外，还介绍了合成葡萄糖吡喃糖苷的N-烷基和N,N-二烷基衍生物。对这些衍生物的抗菌和抗真菌活性评估表明，它们对革兰氏阴性菌没有抑制活性，而许多经过测试的N-烷基皂苷被发现抑制了革兰氏阳性菌和人类病原真菌的生长。
• 1H and13C NMR and X-ray diffraction data for a diosgenylN,O-protected glucopyranoside
  作者：Henryk Myszka、Dorota Bednarczyk、Zbigniew Ciunik、Wies?aw Kaca

  DOI：10.1002/mrc.981

  日期：2002.3

  The assignments of 1H and 13C NMR chemical shifts together with x‐ray diffraction data for synthesized diosgenyl 3,4,6‐tri‐O‐acetyl‐2‐deoxy‐2‐tetrachlorophthalimido‐β‐D‐glucopyranoside are described. The structure of this glycoside was established by using homo‐ and heteronuclear two‐dimensional NMR techniques. X‐ray diffraction data for this compound are also reported. Copyright © 2002 John Wiley

  描述了合成的二萜基 3,4,6-三-O-乙酰基-2-脱氧-2-四氯邻苯二甲酰亚胺-β-D-吡喃葡萄糖苷的 1H 和 13C NMR 化学位移以及 X 射线衍射数据。该糖苷的结构是通过使用同核和异核二维核磁共振技术确定的。还报告了该化合物的 X 射线衍射数据。版权所有 © 2002 John Wiley & Sons, Ltd.
• Differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-d-glucopyranosyl chlorides and their application in the synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside
  作者：Dorota Bednarczyk、Agata Walczewska、Daria Grzywacz、Artur Sikorski、Beata Liberek、Henryk Myszka

  DOI：10.1016/j.carres.2012.11.020

  日期：2013.2

  Four differently N-protected 3,4,6-tri-O-acetyl-2-amino-2-deoxy-D-glucopyranosyl chlorides were synthesized and used as glycosyl donors in reactions with diosgenin. The following amine group protections were tested: trifluoroacetyl (TFA), 2,2,2-trichloroethoxycarbonyl (Troc), phthaloyl (Phth), and tetrachlorophthaloyl (TCP). Products of glycosylation were deprotected to yield diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside. The efficiency of the procedures is discussed. Additionally, a single-crystal X-ray diffraction analysis for 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranosyl chloride is reported. Orientations of the pyranose substituents as well as the planarity of the acetoxy and phthalimide groups in the crystal lattice are discussed. Structural evidence is presented for a mesomeric effect in both groups. The preference of the cis over trans orientation of the acetoxy group is confirmed in the crystal lattice. (C) 2012 Elsevier Ltd. All rights reserved.
• The synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride
  作者：Dorota Bednarczyk、Wiesław Kaca、Henryk Myszka、Lilianna Serwecińska、Zygfryd Smiatacz、Andrzej Zaborowski

  DOI：10.1016/s0008-6215(00)00199-3

  日期：2000.9

  The N-trifluoroacetyl- and N-tetrachlorophthaloyl-protected bromide of D-glucosamine has been used for the first time as a glycosyl donor for the glycosylation of diosgenin [(25R)-spirost-5-en-3 beta-ol]. Both 1,3,4,6-tetra-O-acetyl-2-deoxy-2-trifluoroacetamido-beta-D-glucopyranoside and 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-alpha,beta-D-glucopyranoside were transformed into the appropriate glycosyl bromides. These reacted with diosgenin under mild conditions, using silver triflate as a promoter, and gave the corresponding protected diosgenyl glycosides. Each was deprotected to give diosgenyl 2-amino-2-deoxy-beta-D-glucopyranoside hydrochloride. The structures of the new glycosides were established by H-1 NMR spectroscopy. (C) 2000 Elsevier Science Ltd. All rights reserved.