(Z)-7-Acetoxy-1-<(3-acetoxy-4-methoxyphenyl)methylene>-2-acetyl-6-methoxy-1,2,3,4-tetrahydroisoquinoline | 104621-41-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (Z)-7-Acetoxy-1-<(3-acetoxy-4-methoxyphenyl)methylene>-2-acetyl-6-methoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (Z)-N-acetyl-7-acetoxy-1-(3-acetoxy-4-methoxyphenylmethylene)-6-methoxy-1,2,3,4-tetrahydroisoquinoline；[5-[(Z)-(2-acetyl-7-acetyloxy-6-methoxy-3,4-dihydroisoquinolin-1-ylidene)methyl]-2-methoxyphenyl] acetate
• CAS: 104621-41-2
• 化学式: C₂₄H₂₅NO₇
• 分子量: 439.465
• InChiKey: UKBYRWSAXSDSRD-JMIUGGIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  91.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-7-Acetoxy-1-<(3-acetoxy-4-methoxyphenyl)methylene>-2-acetyl-6-methoxy-1,2,3,4-tetrahydroisoquinoline 以 乙醇 、 二氯甲烷 为溶剂， 以88%的产率得到(R)-N-acetyl-7-acetoxy-1-(3-acetoxy-4-methoxyphenylmethyl)-6-methoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Process for preparing N-acyltetrahydroisoquinoline

  摘要：

  一种制备式（II）所示的N-酰基四氢异喹啉的方法，其中A代表取代有羟基、较低的烷氧基、乙酰氧基或苄氧基的苯环；R代表氢原子、较低的烷基或苯基；X代表氢原子、苯基或取代有羟基、较低的烷氧基或乙酰氧基的苯基，该方法包括在手性铑膦配合物催化剂存在下不对称氢化式（I）所示的N-酰基-1-甲基四氢异喹啉或N-酰基-1-苄基亚甲基四氢异喹啉，其中A、R和X如上所述。该方法可高效纯净地提供N-酰基四氢异喹啉的有用异构体，该异构体可用作合成异喹啉类生物碱药物的中间体，而不需要进行外消旋的光学分辨。

  公开号：

  US04851537A1
• 作为产物：
  描述：

  1,2-dehydronorreticuline 、 乙酸酐 在 吡啶 作用下， 反应 4.0h， 以62%的产率得到(Z)-7-Acetoxy-1-<(3-acetoxy-4-methoxyphenyl)methylene>-2-acetyl-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

• Asymmetric synthesis of isoquinoline alkaloids by homogeneous catalysis
  作者：Ryoji. Noyori、Masako. Ohta、Yi. Hsiao、Masato. Kitamura、Tetsuo. Ohta、Hidemasa. Takaya

  DOI：10.1021/ja00282a054

  日期：1986.10
• US4851537A
  申请人：——

  公开号：US4851537A

  公开（公告）日：1989-07-25