Methyl trans-2-hydroxymethylcyclohexane-1-carboxylate | 171231-24-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl trans-2-hydroxymethylcyclohexane-1-carboxylate
• 英文别名: methyl (1R,2R)-2-(hydroxymethyl)cyclohexane-1-carboxylate
• CAS: 171231-24-6
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: KZNXMMWIDJRYAG-JGVFFNPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl trans-2-hydroxymethylcyclohexane-1-carboxylate 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以81%的产率得到3a,7a-trans-3a,4,5,6,7,7a-Hexahydro-1H-isobenzofuran-3-one
  参考文献：
  名称：

  Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene Reaction

  摘要：

  A concise enantioselective total synthesis of the recently isolated antibacterial and antifungal marine alkaloid (-)-papuamine (1) is described. The key feature of the synthesis includes the development and subsequent implementation of a novel pericyclic imino ene reaction. Starting from readily available enantiomerically pure acid ester 11, allenyl silane N-benzyl imines 24 and 27 were generated in situ from aldehydes 23a/b. These imines undergo concerted stereospecific imino ene reactions to afford silyl acetylenes 25 and 28, respectively, in high yields. The ene reactions were found to be promoted both thermally in refluxing toluene and at lower temperatures using the Lewis acid stannic chloride as a catalyst. Desilylation of compounds 25 and 28 afforded terminal alkynes 26 and 29, respectively, whose structures and stereochemistry were unambiguously established by single crystal X-ray structure analysis of the corresponding HCl salts. In a more highly convergent approach to the alkaloid 1, aldehyde allenyl silane 23a was treated with 0.5 equiv of 1,3-diaminopropane in refluxing toluene to afford homopropargylic diamine 40 as one stereoisomer via a double imino ene reaction, which effectively established the remaining four of the eight stereogenic centers of papuamine in one simple operation. To complete the route to the natural enantiomer of papuamine, a Pd(II) catalyzed macrocyclization of bis-E-vinyl stannane 42b was effected in moderate yield.

  DOI：

  10.1021/ja00149a013
• 作为产物：
  描述：

  cyclohexane-1,2-dicarboxylic acid monomethyl ester 在 硼烷四氢呋喃络合物 、 sodium 作用下， 以 甲醇 为溶剂， 反应 122.0h， 生成 Methyl trans-2-hydroxymethylcyclohexane-1-carboxylate
  参考文献：
  名称：

  Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene Reaction

  摘要：

  A concise enantioselective total synthesis of the recently isolated antibacterial and antifungal marine alkaloid (-)-papuamine (1) is described. The key feature of the synthesis includes the development and subsequent implementation of a novel pericyclic imino ene reaction. Starting from readily available enantiomerically pure acid ester 11, allenyl silane N-benzyl imines 24 and 27 were generated in situ from aldehydes 23a/b. These imines undergo concerted stereospecific imino ene reactions to afford silyl acetylenes 25 and 28, respectively, in high yields. The ene reactions were found to be promoted both thermally in refluxing toluene and at lower temperatures using the Lewis acid stannic chloride as a catalyst. Desilylation of compounds 25 and 28 afforded terminal alkynes 26 and 29, respectively, whose structures and stereochemistry were unambiguously established by single crystal X-ray structure analysis of the corresponding HCl salts. In a more highly convergent approach to the alkaloid 1, aldehyde allenyl silane 23a was treated with 0.5 equiv of 1,3-diaminopropane in refluxing toluene to afford homopropargylic diamine 40 as one stereoisomer via a double imino ene reaction, which effectively established the remaining four of the eight stereogenic centers of papuamine in one simple operation. To complete the route to the natural enantiomer of papuamine, a Pd(II) catalyzed macrocyclization of bis-E-vinyl stannane 42b was effected in moderate yield.

  DOI：

  10.1021/ja00149a013

文献信息

• Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene Reaction
  作者：Robert M. Borzilleri、Steven M. Weinreb、Masood Parvez

  DOI：10.1021/ja00149a013

  日期：1995.11

  A concise enantioselective total synthesis of the recently isolated antibacterial and antifungal marine alkaloid (-)-papuamine (1) is described. The key feature of the synthesis includes the development and subsequent implementation of a novel pericyclic imino ene reaction. Starting from readily available enantiomerically pure acid ester 11, allenyl silane N-benzyl imines 24 and 27 were generated in situ from aldehydes 23a/b. These imines undergo concerted stereospecific imino ene reactions to afford silyl acetylenes 25 and 28, respectively, in high yields. The ene reactions were found to be promoted both thermally in refluxing toluene and at lower temperatures using the Lewis acid stannic chloride as a catalyst. Desilylation of compounds 25 and 28 afforded terminal alkynes 26 and 29, respectively, whose structures and stereochemistry were unambiguously established by single crystal X-ray structure analysis of the corresponding HCl salts. In a more highly convergent approach to the alkaloid 1, aldehyde allenyl silane 23a was treated with 0.5 equiv of 1,3-diaminopropane in refluxing toluene to afford homopropargylic diamine 40 as one stereoisomer via a double imino ene reaction, which effectively established the remaining four of the eight stereogenic centers of papuamine in one simple operation. To complete the route to the natural enantiomer of papuamine, a Pd(II) catalyzed macrocyclization of bis-E-vinyl stannane 42b was effected in moderate yield.