Ethyl (3R,4aS,8aS)-2-(methoxycarbonyl)-6-(methoxymethylidene)-1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline-3-carboxylate | 159406-71-0

• 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: Ethyl (3R,4aS,8aS)-2-(methoxycarbonyl)-6-(methoxymethylidene)-1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline-3-carboxylate
• CAS: 159406-71-0
• 化学式: C₁₆H₂₅NO₅
• 分子量: 311.378
• InChiKey: DTGPDFOVXYXAFI-HZSPNIEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.34
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  65.07
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Ethyl (3R,4aS,8aS)-2-(methoxycarbonyl)-6-(methoxymethylidene)-1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline-3-carboxylate 在 盐酸 、 sodium tetrahydroborate 作用下， 以 乙醇 、 乙腈 为溶剂， 反应 0.5h， 生成 Ethyl (3R,4aS,6S,8aS)-6-(hydroxymethyl)-2-(methoxycarbonyl)-1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline-3-carboxylate
  参考文献：
  名称：

  Stereoselective Synthesis of 6-Substituted Decahydroisoquinoline-3-carboxylates: Intermediates for the Preparation of Conformationally Constrained Acidic Amino Acids

  摘要：

  In this article we describe the stereoselective preparation of two 6-(hydroxymethyl) substituted decahydroisoquinoline-3-carboxylates, which are useful in the synthesis of a number of excitatory amino acid antagonists, e.g., (-)-1a (LY235959), (-)-2a (LY202157) and (-)-3a(LY293558). For example, the known ketone 4 was converted to either the (3SR,4aRS,6SR,8aRS)-alcohol 18 or the (3SR,4aRS,6RS,8aRS)-alcohol 21, the former via a stereoselective hydroboration reaction, the latter via a stereoselective enol ether hydrolysis followed by reduction. These C-6 epimeric alcohols were easily converted to a number of useful intermediates, e.g., aldehydes, bromides and iodides. If we used resolved ketone 4, then these intermediates could be obtained in optically active form. In either racemic or non-racemic form, these intermediates provided access to a number of diastereomerically pure amino acids that were difficult to obtain by earlier routes.

  DOI：

  10.1021/jo00104a051
• 作为产物：
  描述：

  甲氧基甲基三苯基氯化膦 、 (3R,4aR,8aS)-6-Oxo-octahydro-isoquinoline-2,3-dicarboxylic acid 3-ethyl ester 2-methyl ester 在 sodium hexamethyldisilazane 作用下， 生成 Ethyl (3R,4aS,8aS)-2-(methoxycarbonyl)-6-(methoxymethylidene)-1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline-3-carboxylate
  参考文献：
  名称：

  Stereoselective Synthesis of 6-Substituted Decahydroisoquinoline-3-carboxylates: Intermediates for the Preparation of Conformationally Constrained Acidic Amino Acids

  摘要：

  In this article we describe the stereoselective preparation of two 6-(hydroxymethyl) substituted decahydroisoquinoline-3-carboxylates, which are useful in the synthesis of a number of excitatory amino acid antagonists, e.g., (-)-1a (LY235959), (-)-2a (LY202157) and (-)-3a(LY293558). For example, the known ketone 4 was converted to either the (3SR,4aRS,6SR,8aRS)-alcohol 18 or the (3SR,4aRS,6RS,8aRS)-alcohol 21, the former via a stereoselective hydroboration reaction, the latter via a stereoselective enol ether hydrolysis followed by reduction. These C-6 epimeric alcohols were easily converted to a number of useful intermediates, e.g., aldehydes, bromides and iodides. If we used resolved ketone 4, then these intermediates could be obtained in optically active form. In either racemic or non-racemic form, these intermediates provided access to a number of diastereomerically pure amino acids that were difficult to obtain by earlier routes.

  DOI：

  10.1021/jo00104a051