(1R,3R,6S,7S,9S,10S)-3-methoxy-9-methyl-8-oxatetracyclo[7.2.1.17,10.01,6]tridecan-4-one | 1256640-11-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1R,3R,6S,7S,9S,10S)-3-methoxy-9-methyl-8-oxatetracyclo[7.2.1.17,10.01,6]tridecan-4-one
• CAS: 1256640-11-5
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: BPOKLCYTJFAWTM-FJPLXSFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  在 10% palladium on activated carbon 、 氢气 、 potassium hydroxide 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 1.5h， 以15.7 mg的产率得到(1R,3R,6S,7S,9S,10S)-3-methoxy-9-methyl-8-oxatetracyclo[7.2.1.17,10.01,6]tridecan-4-one
  参考文献：
  名称：

  A Bismuth(III)-Catalyzed Friedel−Crafts Cyclization and Stereocontrolled Organocatalytic Approach to (−)-Platensimycin

  摘要：

  A high yielding route to the (-)-platensimycin core is communicated. This entailed the discovery of Bi(OTf)(3) to catalyze a Friedel-Crafts cyclization of a free lactol, supplemented by LiClO4 to suppress the Lewis basicity of the sulfonate group. After TBAF-promotecl cyclodearomatization, a diastereoselective conjugate reduction of a dienone was achieved by adopting amine-based organocatalytic rationales to reverse the inherent steric control of the substrate.

  DOI：

  10.1021/ol102390t

文献信息

• Total Synthesis of (−)-Platensimycin by Advancing Oxocarbenium- and Iminium-Mediated Catalytic Methods
  作者：Stanley T.-C. Eey、Martin J. Lear

  DOI：10.1002/chem.201400131

  日期：2014.9.1

  synthetic advances include 1) a modified Lieben haloform reaction to directly convert an aryl methyl ketone into its methyl ester within 30 seconds, 2) an experimentally improved dialkylation protocol to form platensic acid, 3) a sterically controlled chemo‐ and diastereoselective organocatalytic conjugate reduction of a spiro‐cyclized cyclohexadienone by using the trifluoroacetic acid salt of α‐amino di‐tert‐butyl

  （−）‐ Platensimycin是有效的脂肪酸合酶抑制剂，在治疗代谢性疾病（例如糖尿病和“脂肪肝”）和病原性感染（例如由耐药细菌引起的感染）方面具有广阔的前景。在此，我们通过四步制备芳香胺片段和改进的立体异构控制的酮内酯片段（-）-戊酸来描述其总合成。关键的合成进展包括：1）改进的Lieben卤仿反应，可在30秒内将芳基甲基酮直接转化为甲酯； 2）经过实验改进的二烷基化方案形成了膦酸； 3）立体控制的化学和非对映选择性有机催化共轭还原α-氨基二氨基三氟乙酸盐制备螺环化环己二酮丙二酸叔丁酯，4）氟化四丁基铵促进游离酚的螺-烷基化对位脱芳香化反应，以具有早期甲苯磺酸酯中间体的适度离去能力的方式组装笼状酮内酯，以及5）铋（III）催化的Friedel –以LiClO 4为添加剂，进行游离乳醇的环化反应，以释放出活性更高的高碳氧碳鎓物种，并抑制了磺酰氧基的Lewis碱度。最长的线性序列为21个
• A Bismuth(III)-Catalyzed Friedel−Crafts Cyclization and Stereocontrolled Organocatalytic Approach to (−)-Platensimycin
  作者：Stanley T.-C. Eey、Martin J. Lear

  DOI：10.1021/ol102390t

  日期：2010.12.3

  A high yielding route to the (-)-platensimycin core is communicated. This entailed the discovery of Bi(OTf)(3) to catalyze a Friedel-Crafts cyclization of a free lactol, supplemented by LiClO4 to suppress the Lewis basicity of the sulfonate group. After TBAF-promotecl cyclodearomatization, a diastereoselective conjugate reduction of a dienone was achieved by adopting amine-based organocatalytic rationales to reverse the inherent steric control of the substrate.