1,6-Anhydro-2,3-di-O-benzyl-β-D-gluco-hexopyrano-4-ulose | 138709-45-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,6-Anhydro-2,3-di-O-benzyl-β-D-gluco-hexopyrano-4-ulose
• 英文别名: 1,6-anhydro-2,3-di-O-benzyl-β-D-xylo-hexopyranos-4-ulose；1,6-anhydro-2,3-di-O-benzyl-β-D-ribohexopyranos-4-ulose；(1R,3R,4R,5R)-3,4-bis(phenylmethoxy)-6,8-dioxabicyclo[3.2.1]octan-2-one
• CAS: 138709-45-2
• 化学式: C₂₀H₂₀O₅
• 分子量: 340.376
• InChiKey: IJJLESWSBKJAJP-GSEOLPGOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,6-Anhydro-2,3-di-O-benzyl-β-D-gluco-hexopyrano-4-ulose 在 palladium dihydroxide 咪唑 、 盐酸 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 、 重铬酸吡啶 、 cerium(III) chloride 、 2-甲基-2-丁烯 、 二甲基硫 、 Celite 、 四丁基氟化铵 、 氢气 、 双氧水 、 叔丁基锂 、 sodium methylate 、 4-甲基苯磺酸吡啶 、 乙酸酐 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 对甲苯磺酸 、 臭氧 、 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 74.33h， 生成 (1S-(1α,3α,4β,5α,6α,7β))-1-(3,3-dimethoxypropyl)-4,6,7-trihydroxy-2,8-dioxabicyclo[3.2.1]octane-3,4,5-tricarboxylic acid 3,4,5-tris(1,1-dimethylethyl) ester
  参考文献：
  名称：

  Total Synthesis of Zaragozic Acid A (Squalestatin S1). Synthesis of the Relay Compound

  摘要：

  Compound 2 has been prepared from the 1,6-anhydropyranohexose 3. The key process for elaborating the 1,7-dioxabicyclo[3.2.1]octane core of the zaragozic acids is addition of an organometallic reagent to lactone 6 and treatment of the resulting 1,2,3-trihydroxy-6-oxo ethylene acetal with acid. Use of the cerium(III) reagent of 4-bromo-1-butene in this process provided 7 in excellent yield, unaccompanied by the isomeric 1,6-anhydropyranose isomer. The remaining two carboxy groups of the zaragozic acid core were added by addition of the lithium enolate of 8 to formaldehyde, to obtain 9, and cerium(III)-mediated addition of vinyllithium to ketone 10. The latter addition was shown by 2D H-1 NMR experiments to provide the relative configuration found in the zaragozic acids. Similar stereoselective additions were observed with 2-furyllithium and (5-methyl-2-furyl)-lithium, but the resulting adducts are resistant to ozonolysis. The synthesis of 2 completes a total synthesis of zaragozic acid A (squalestatin S1) (1).

  DOI：

  10.1021/jo961534e
• 作为产物：
  描述：

  1,6-Anhydro-2,3-di-O-benzyl-β-D-galactopyranose 在 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 生成 1,6-Anhydro-2,3-di-O-benzyl-β-D-gluco-hexopyrano-4-ulose
  参考文献：
  名称：

  Synthesis of 1-Substituted and 1,4-Disubstituted 2,3-Di-O-benzyl-1,6-anhydrogalactofuranoses

  摘要：

  A method has been developed for synthesizing 1-substituted and 1,4-disubstituted 2,3-di-O-benzyl-1,6-anhydrogalactofuranoses 16 starting from 8, a known 1,6-anhydropyranose prepared from D-galactose. Compounds such as 16 have potential utility for synthesis of the squalestatins and zaragozic acids.

  DOI：

  10.1021/jo00114a028

文献信息

• An improved synthesis of 1,6-anhydro-2,3-di-O-benzyl-β-d-xylo-hexopyranos-4-ulose
  作者：Stéphane Caron、Andrew I. McDonald、Clayton H. Heathcock

  DOI：10.1016/0008-6215(95)00335-5

  日期：1996.2
• Total Synthesis of Zaragozic Acid A (Squalestatin S1). Synthesis of the Relay Compound
  作者：Stéphane Caron、Doris Stoermer、Anna Kathryn Mapp、Clayton H. Heathcock

  DOI：10.1021/jo961534e

  日期：1996.1.1

  Compound 2 has been prepared from the 1,6-anhydropyranohexose 3. The key process for elaborating the 1,7-dioxabicyclo[3.2.1]octane core of the zaragozic acids is addition of an organometallic reagent to lactone 6 and treatment of the resulting 1,2,3-trihydroxy-6-oxo ethylene acetal with acid. Use of the cerium(III) reagent of 4-bromo-1-butene in this process provided 7 in excellent yield, unaccompanied by the isomeric 1,6-anhydropyranose isomer. The remaining two carboxy groups of the zaragozic acid core were added by addition of the lithium enolate of 8 to formaldehyde, to obtain 9, and cerium(III)-mediated addition of vinyllithium to ketone 10. The latter addition was shown by 2D H-1 NMR experiments to provide the relative configuration found in the zaragozic acids. Similar stereoselective additions were observed with 2-furyllithium and (5-methyl-2-furyl)-lithium, but the resulting adducts are resistant to ozonolysis. The synthesis of 2 completes a total synthesis of zaragozic acid A (squalestatin S1) (1).
• Synthesis of 1-Substituted and 1,4-Disubstituted 2,3-Di-O-benzyl-1,6-anhydrogalactofuranoses
  作者：Stephane Caron、Andrew I. McDonald、Clayton H. Heathcock

  DOI：10.1021/jo00114a028

  日期：1995.5

  A method has been developed for synthesizing 1-substituted and 1,4-disubstituted 2,3-di-O-benzyl-1,6-anhydrogalactofuranoses 16 starting from 8, a known 1,6-anhydropyranose prepared from D-galactose. Compounds such as 16 have potential utility for synthesis of the squalestatins and zaragozic acids.