methyl (1R,3S)-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate | 1219687-58-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: methyl (1R,3S)-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate
• 英文别名: (1R,3S)-Methyl 2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate；methyl (1R,3S)-2-benzyl-6,7-dimethoxy-1-phenyl-3,4-dihydro-1H-isoquinoline-3-carboxylate
• CAS: 1219687-58-7
• 化学式: C₂₆H₂₇NO₄
• 分子量: 417.505
• InChiKey: ZOLIBKRXIMBIQP-WIOPSUGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (1R,3S)-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate 在 10% palladium on activated charcoal 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 ((1R,3S)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinolin-3-yl)diphenylmethanol
  参考文献：
  名称：

  Novel tetrahydroisoquinoline based organocatalysts for asymmetric Diels–Alder reactions: insight into the catalytic mode using ROESY NMR and DFT studies

  摘要：

  For the first time an organocatalyst bearing a secondary nitrogen within a cyclohexane ring has been evaluated in the asymmetric Diels-Alder reaction. This organocatalyst is also the first of its kind based on a (1R,3S)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline backbone. These catalysts were tested over a range of dienes and dienophiles and displayed promising chemical conversions of up to 100% with up to 64% ee with triflic acid as the cocatalyst. Density functional theory computational studies and 20 NMR spectroscopy were used to determine the structure of the intermediate iminium ion formed between the most efficient catalyst and cinnamaldehyde. The reaction profile for each of the four possibilities in this reaction were calculated and it was found that the iminium intermediate leading to the major product is higher in energy but kinetically preferred. The activation energies of all possible reaction paths were calculated and the results correlated with the observed products. These experiments revealed that the presence of both (E)- and (Z)-isomers of the cinnamaldehyde were contributing factors for the low enantioselectivity of the reaction products. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.11.010
• 作为产物：
  描述：

  左旋多巴 在 10% palladium on activated charcoal 、 氢气 、 potassium carbonate 、 potassium hydrogencarbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醇 、 水 、 丙酮 、 乙腈 为溶剂， 生成 methyl (1R,3S)-2-benzyl-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylate
  参考文献：
  名称：

  Novel tetrahydroisoquinoline based organocatalysts for asymmetric Diels–Alder reactions: insight into the catalytic mode using ROESY NMR and DFT studies

  摘要：

  For the first time an organocatalyst bearing a secondary nitrogen within a cyclohexane ring has been evaluated in the asymmetric Diels-Alder reaction. This organocatalyst is also the first of its kind based on a (1R,3S)-6,7-dimethoxy-1-phenyl-1,2,3,4-tetrahydroisoquinoline backbone. These catalysts were tested over a range of dienes and dienophiles and displayed promising chemical conversions of up to 100% with up to 64% ee with triflic acid as the cocatalyst. Density functional theory computational studies and 20 NMR spectroscopy were used to determine the structure of the intermediate iminium ion formed between the most efficient catalyst and cinnamaldehyde. The reaction profile for each of the four possibilities in this reaction were calculated and it was found that the iminium intermediate leading to the major product is higher in energy but kinetically preferred. The activation energies of all possible reaction paths were calculated and the results correlated with the observed products. These experiments revealed that the presence of both (E)- and (Z)-isomers of the cinnamaldehyde were contributing factors for the low enantioselectivity of the reaction products. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.11.010

文献信息

• Synthesis and Screening of C¹-Substituted Tetrahydroisoquinoline Derivatives for Asymmetric Transfer Hydrogenation Reactions
  作者：Sai Kumar Chakka、Pher G. Andersson、Glenn E. M. Maguire、Hendrik G. Kruger、Thavendran Govender

  DOI：10.1002/ejoc.200901159

  日期：2010.2

  Tetrahydroisoquinoline (TIQ) derivatives exhibit good biological activity. However, utilization of TIQ compounds in asymmetric catalysis is limited. This paper presents a series of TIQ derivatives in asymmetric transfer hydrogenation (ATH) reactions. Chiral TIQ amino alcohol ligands were synthesized and screened for the ATH reaction of aromatic ketones. The effect of a cis- and trans-phenyl substitution

  四氢异喹啉 (TIQ) 衍生物表现出良好的生物活性。然而，TIQ 化合物在不对称催化中的应用是有限的。本文介绍了一系列用于不对称转移氢化 (ATH) 反应的 TIQ 衍生物。合成了手性 TIQ 氨基醇配体并筛选了芳香酮的 ATH 反应。通过实验和计算研究了 C-1 位置上的顺式和反式苯基取代对配体骨架的影响。结果表明，在室温下用 Ru 复合物获得的 TIQ 支架上的反式取向产生更高的周转率，选择性为 94% ee。顺式异构体导致没有选择性的高周转率。反式异构体在较低温度下产生 99% ee。此外，