(1S,3S,4R,5R,6R,7R)-1-but-3-enyl-4-(furan-2-yl)-4-hydroxy-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octane-3,5-dicarboxylic acid | 1054610-04-6

• 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: (1S,3S,4R,5R,6R,7R)-1-but-3-enyl-4-(furan-2-yl)-4-hydroxy-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octane-3,5-dicarboxylic acid
• CAS: 1054610-04-6
• 化学式: C₃₀H₃₀O₁₀
• 分子量: 550.562
• InChiKey: HBYKTKSAEJPYIV-SIYOOCKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  145
• 氢给体数：
  3
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2-叔丁基-1,3-二异丙基异脲 、 (1S,3S,4R,5R,6R,7R)-1-but-3-enyl-4-(furan-2-yl)-4-hydroxy-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octane-3,5-dicarboxylic acid 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 ditert-butyl (1S,3S,4R,5R,6R,7R)-1-but-3-enyl-4-(furan-2-yl)-4-hydroxy-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octane-3,5-dicarboxylate
  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：

  (1S,3R,5R,6R,7R)-1-but-3-enyl-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-(hydroxymethyl)-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octan-4-one 在 咪唑 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 四丁基氟化铵 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 4.25h， 生成 (1S,3S,4R,5R,6R,7R)-1-but-3-enyl-4-(furan-2-yl)-4-hydroxy-6,7-bis(phenylmethoxy)-2,8-dioxabicyclo[3.2.1]octane-3,5-dicarboxylic acid
  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

文献信息

• 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).