3-hydroxy-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxa-tricyclo-[13.3.1.0(5,10)]nonadeca-5,7,9-trien-11-one | 1301247-81-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: 3-hydroxy-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxa-tricyclo-[13.3.1.0(5,10)]nonadeca-5,7,9-trien-11-one
• 英文别名: 3-Hydroxy-7,9,16-tris-methoxymethoxy-13-methyl-12,19-dioxa-tricyclo[13.3.1.0 (5,10)]nonadeca-5,7,9-trien-11-one；(1S,3S,13S,15R,16S)-3-hydroxy-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxatricyclo[13.3.1.05,10]nonadeca-5(10),6,8-trien-11-one
• CAS: 1301247-81-3
• 化学式: C₂₄H₃₆O₁₀
• 分子量: 484.544
• InChiKey: QEHZQUJWOBOBII-NMKBPFOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  111
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3-hydroxy-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxa-tricyclo-[13.3.1.0(5,10)]nonadeca-5,7,9-trien-11-one 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到(1S,13S,15R,16S)-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxatricyclo[13.3.1.05,10]nonadeca-5(10),6,8-triene-3,11-dione
  参考文献：
  名称：

  Synthesis of the Purported ent-Pochonin J Structure Featuring a Stereoselective Oxocarbenium Allylation

  摘要：

  The synthesis of the alleged natural product pochonin J is presented. Key steps of this convergent synthesis include a chemoselective Wacker oxidation, and an Evans' anti-reduction of the resulting ketone. Upon ozonolysis, this intermediate undergoes a 6-exo-trig cyclization to give a hemiketal intermediate, the key oxocarbenium precursor. The construction of the alpha-C-glycoside subunit is highlighted by a mismatched oxocarbenium cation formation/allylation sequence. An olefin metathesis afforded the 14-membered macrolactone, and final oxidation provided the "desired" compound that does not spectroscopically correlate to the initially described natural product.

  DOI：

  10.1021/jo200332d
• 作为产物：
  描述：

  2,4,6-三羟基苯甲酸 在 吡啶 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4-二甲氨基吡啶 、 氯化亚砜 、 PdCl2(dppf)*CHCl3 、 palladium 10% on activated carbon 、 氢气 、 四丁基碘化铵 、 sodium hydride 、 碳酸氢钠 、 potassium carbonate 、 三乙胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 109.0h， 生成 3-hydroxy-7,9,16-tris(methoxymethoxy)-13-methyl-12,19-dioxa-tricyclo-[13.3.1.0(5,10)]nonadeca-5,7,9-trien-11-one
  参考文献：
  名称：

  Synthesis of the Purported ent-Pochonin J Structure Featuring a Stereoselective Oxocarbenium Allylation

  摘要：

  The synthesis of the alleged natural product pochonin J is presented. Key steps of this convergent synthesis include a chemoselective Wacker oxidation, and an Evans' anti-reduction of the resulting ketone. Upon ozonolysis, this intermediate undergoes a 6-exo-trig cyclization to give a hemiketal intermediate, the key oxocarbenium precursor. The construction of the alpha-C-glycoside subunit is highlighted by a mismatched oxocarbenium cation formation/allylation sequence. An olefin metathesis afforded the 14-membered macrolactone, and final oxidation provided the "desired" compound that does not spectroscopically correlate to the initially described natural product.

  DOI：

  10.1021/jo200332d

文献信息

• Synthesis of the Purported <i>ent</i>-Pochonin J Structure Featuring a Stereoselective Oxocarbenium Allylation
  作者：Dionicio Martinez-Solorio、Kenneth A. Belmore、Michael P. Jennings

  DOI：10.1021/jo200332d

  日期：2011.5.20

  The synthesis of the alleged natural product pochonin J is presented. Key steps of this convergent synthesis include a chemoselective Wacker oxidation, and an Evans' anti-reduction of the resulting ketone. Upon ozonolysis, this intermediate undergoes a 6-exo-trig cyclization to give a hemiketal intermediate, the key oxocarbenium precursor. The construction of the alpha-C-glycoside subunit is highlighted by a mismatched oxocarbenium cation formation/allylation sequence. An olefin metathesis afforded the 14-membered macrolactone, and final oxidation provided the "desired" compound that does not spectroscopically correlate to the initially described natural product.