(R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline | 154013-19-1

• 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: (R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (1R)-1-[(3-hydroxy-4-methoxyphenyl)methyl]-6-methoxy-3,4-dihydro-1H-isoquinoline-2-carbaldehyde
• CAS: 154013-19-1
• 化学式: C₁₉H₂₁NO₄
• 分子量: 327.38
• InChiKey: PTXRBHLQGUWMEQ-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  59
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline 在 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 15.0h， 生成 (+)-(R)-1-(3-hydroxy-4-methoxybenzyl)-6-methoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes

  摘要：

  In the presence of a small amount of RuX(2)[(R)- or (S)-BINAP] (X = anionic ligand) a wide range of (Z)-2-acyl-1-benzylidene-1,2,3,4-tetrahydroisoquinolines are hydrogenated to give the saturated products in nearly quantitative yields and in high (up to 100 %) optical yields. The enamide substrates are selectively prepared by N-acylation of the corresponding 1-benzylated 3,4-dihydroisoquinolines under suitable acylation conditions; some crystalline materials having low solubility are obtained by a second-order Z/E stereomutation technique utilizing the double-bond photolability and lattice energy effects. This asymmetric hydrogenation sets the key stereogenic center in a predictable manner, either R or S flexibly, at the C(1) position of the benzylated tetrahydroisoquinolines. The chiral products are converted by standard functional group modification to tetrahydropapaverine, laudanosine, tretoquinol, norreticuline, etc. Hydrogenation of the simple 1-methylene substrate is used fbr synthesis of salsolidine. This enantioselective hydrogenation is applied to the synthesis of morphine and its artificial analogues such as morphinans and benzomorphans of either chirality. A mnemonic device is presented for predicting the reactivity and enantiofacial selection of the BINAP-Ru catalyzed hydrogenation. Reaction with BINAP-Rh catalyst proceeds with a lower enantioselectivity and an opposite sense of asymmetric induction.

  DOI：

  10.1021/jo00081a007
• 作为产物：
  描述：

  在 Ru<(R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl>(OCOCH3)2 ammonium hydroxide 、 氢气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 25.0 ℃ 、5.07 MPa 条件下， 反应 98.0h， 生成 (R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes

  摘要：

  In the presence of a small amount of RuX(2)[(R)- or (S)-BINAP] (X = anionic ligand) a wide range of (Z)-2-acyl-1-benzylidene-1,2,3,4-tetrahydroisoquinolines are hydrogenated to give the saturated products in nearly quantitative yields and in high (up to 100 %) optical yields. The enamide substrates are selectively prepared by N-acylation of the corresponding 1-benzylated 3,4-dihydroisoquinolines under suitable acylation conditions; some crystalline materials having low solubility are obtained by a second-order Z/E stereomutation technique utilizing the double-bond photolability and lattice energy effects. This asymmetric hydrogenation sets the key stereogenic center in a predictable manner, either R or S flexibly, at the C(1) position of the benzylated tetrahydroisoquinolines. The chiral products are converted by standard functional group modification to tetrahydropapaverine, laudanosine, tretoquinol, norreticuline, etc. Hydrogenation of the simple 1-methylene substrate is used fbr synthesis of salsolidine. This enantioselective hydrogenation is applied to the synthesis of morphine and its artificial analogues such as morphinans and benzomorphans of either chirality. A mnemonic device is presented for predicting the reactivity and enantiofacial selection of the BINAP-Ru catalyzed hydrogenation. Reaction with BINAP-Rh catalyst proceeds with a lower enantioselectivity and an opposite sense of asymmetric induction.

  DOI：

  10.1021/jo00081a007

文献信息

• SUBSTITUTED BERBINES AND THEIR SYNTHESIS
  申请人：MALLINCKRODT LLC

  公开号：US20150099772A1

  公开（公告）日：2015-04-09

  The present invention provides substituted berbines, processes for the synthesis of substituted berbine compounds, as well as intermediates used in the synthesis of substituted berbine compounds. Also provided are methods for using the substituted berbines to inhibit cancer cell growth.

  本发明提供了替代苯并啉化合物，以及用于合成替代苯并啉化合物的工艺，以及合成替代苯并啉化合物所使用的中间体。还提供了使用替代苯并啉来抑制癌细胞生长的方法。