diosgenyl 2-deoxy-2-trifluoroacetamido-β-D-glucospyranoside

• 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 2-deoxy-2-trifluoroacetamido-β-D-glucospyranoside
• 英文别名: diosgenyl 2-deoxy-2-trifluoroacetamido-β-D-glucopyranoside；N-[(2R,3R,4R,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-2-[(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-3-yl]-2,2,2-trifluoroacetamide
• 化学式: C₃₅H₅₂F₃NO₈
• 分子量: 671.795
• InChiKey: LXFMBRCKGJRKJO-GFNCHACNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  47
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  127
• 氢给体数：
  4
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  diosgenyl 2-deoxy-2-trifluoroacetamido-β-D-glucospyranoside 在 sodium hydroxide 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 以80%的产率得到diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.carres.2012.11.020
• 作为产物：
  描述：

  薯蓣皂素 在 sodium methylate 、 silver trifluoromethanesulfonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 diosgenyl 2-deoxy-2-trifluoroacetamido-β-D-glucospyranoside
  参考文献：
  名称：

  The synthesis of diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride

  摘要：

  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.

  DOI：

  10.1016/s0008-6215(00)00199-3

文献信息

• Synthesis and induction of apoptosis in B cell chronic leukemia by diosgenyl 2-amino-2-deoxy-β-d-glucopyranoside hydrochloride and its derivatives
  作者：Henryk Myszka、Dorota Bednarczyk、Maria Najder、Wiesław Kaca

  DOI：10.1016/s0008-6215(02)00407-x

  日期：2003.1

  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.
• 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.