methyl 3-C-cyano-3-deoxy-3-ethoxycarbonyl-β-D-glucopyranoside | 391208-39-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-C-cyano-3-deoxy-3-ethoxycarbonyl-β-D-glucopyranoside
• 英文别名: ethyl (2R,3S,4S,5R,6R)-4-cyano-3,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxane-4-carboxylate
• CAS: 391208-39-2
• 化学式: C₁₁H₁₇NO₇
• 分子量: 275.258
• InChiKey: IVNUMXMUEMLJJZ-DZEUPHNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  129
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 3-C-cyano-3-deoxy-3-ethoxycarbonyl-β-D-glucopyranoside 在 4,4'-二氨基二苯乙烯-2,2'-二磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以34%的产率得到methyl 3-C-cyano-3,6-dideoxy-3-ethoxycarbonyl-6-fluoro-β-D-glucopyranoside
  参考文献：
  名称：

  Towards cyclic, conformationally constrained, fluorine-containing β-amino acid derivatives from d-glucose

  摘要：

  Novel, potentially bioactive. fluorinated branched-chain monosaccharides were obtained by reaction of diethylaminosulphur trifluoride (DAST) with a series of methyl 3-C-cyano-3-ethoxycarbonyl-beta -D-glucopyranoside derivatives including the 4,6-O-benzylidene derivative and their 3-C-(N-protected aminomethyl) reduction products, as well as the phenyl 3-C-cyano-3-ethoxycarbonyl-1-thio-alpha -D-(and beta -D-)glucopyranosides, The absolute configuration at C(3) was unambiguously assigned for all Compounds on the basis of X-ray crystallographic analysis of methyl 4,6-O-benzylidene-3-C-cyano-3-deoxy-3-ethoxycarbonyl-beta -D-glucopyranoside, corroborating the previous tentative assignment by other authors for the 4,6-unprotected Compound. The course of the fluorination depended on the reaction temperature and the substitution pattern of the Substrate. Thus. for methyl 3-C-cyano-3-ethoxycarbonyl-beta -D-glucopyranoside, fluorination occurred exclusively at C(6), but for the phenylthio analogue. a 2-deoxy-2-phenylthio-alpha -D-manno-configured glycosyl fluoride and its 6-fluoro derivative were obtained, resulting from the expected rearrangement reaction. whilst starting from the phenylthio alpha anomer. only the Unrearranged 6-fluoro compound was formed. Rearrangement was also observed in the fluorination of methyl 4,6-O-benzylidene-3-C-(N-protected aminomethyl)-beta -D-glucopyranoside, which led to the 2-O-methyl-alpha -D-mannopyranosyl fluoride derivative as the sole product. This methodology may constitute a simple route to enantiopure conformationally constrained cyclic fluorinated beta -amino acids having the alpha carbon atom shared with a pyranose ring, although only moderate yields were achieved. particularly in the fluorination step. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00354-8
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-3-C-cyano-3-deoxy-3-ethoxycarbonyl-β-D-glucopyranoside 在 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 3.0h， 以96%的产率得到methyl 3-C-cyano-3-deoxy-3-ethoxycarbonyl-β-D-glucopyranoside
  参考文献：
  名称：

  Towards cyclic, conformationally constrained, fluorine-containing β-amino acid derivatives from d-glucose

  摘要：

  Novel, potentially bioactive. fluorinated branched-chain monosaccharides were obtained by reaction of diethylaminosulphur trifluoride (DAST) with a series of methyl 3-C-cyano-3-ethoxycarbonyl-beta -D-glucopyranoside derivatives including the 4,6-O-benzylidene derivative and their 3-C-(N-protected aminomethyl) reduction products, as well as the phenyl 3-C-cyano-3-ethoxycarbonyl-1-thio-alpha -D-(and beta -D-)glucopyranosides, The absolute configuration at C(3) was unambiguously assigned for all Compounds on the basis of X-ray crystallographic analysis of methyl 4,6-O-benzylidene-3-C-cyano-3-deoxy-3-ethoxycarbonyl-beta -D-glucopyranoside, corroborating the previous tentative assignment by other authors for the 4,6-unprotected Compound. The course of the fluorination depended on the reaction temperature and the substitution pattern of the Substrate. Thus. for methyl 3-C-cyano-3-ethoxycarbonyl-beta -D-glucopyranoside, fluorination occurred exclusively at C(6), but for the phenylthio analogue. a 2-deoxy-2-phenylthio-alpha -D-manno-configured glycosyl fluoride and its 6-fluoro derivative were obtained, resulting from the expected rearrangement reaction. whilst starting from the phenylthio alpha anomer. only the Unrearranged 6-fluoro compound was formed. Rearrangement was also observed in the fluorination of methyl 4,6-O-benzylidene-3-C-(N-protected aminomethyl)-beta -D-glucopyranoside, which led to the 2-O-methyl-alpha -D-mannopyranosyl fluoride derivative as the sole product. This methodology may constitute a simple route to enantiopure conformationally constrained cyclic fluorinated beta -amino acids having the alpha carbon atom shared with a pyranose ring, although only moderate yields were achieved. particularly in the fluorination step. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00354-8