(Z)-2-Acetyl-6,7-bis(benzyloxy)-1-<(3,4,5-trimethoxyphenyl)methylene>-1,2,3,4-tetrahydroisoquinoline | 104621-40-1

• 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)-2-Acetyl-6,7-bis(benzyloxy)-1-<(3,4,5-trimethoxyphenyl)methylene>-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (Z)-N-acetyl-6,7-dibenzyloxy-1-(3,4,5-trimethoxyphenylmethylene)-1,2,3,4-tetrahydroisoquinoline；(Z)-2-Acetyl-6,7-bis(benzyloxy)-1-[(3,4,5-trimethoxyphenyl)methylene]-1,2,3,4-tetrahydroisoquinoline；1-[(1Z)-6,7-bis(phenylmethoxy)-1-[(3,4,5-trimethoxyphenyl)methylidene]-3,4-dihydroisoquinolin-2-yl]ethanone
• CAS: 104621-40-1
• 化学式: C₃₅H₃₅NO₆
• 分子量: 565.666
• InChiKey: LUKXFXXMZQURJD-LQNQUEJISA-N

物化性质

• 沸点：
  748.5±60.0 °C(Predicted)
• 密度：
  1.209±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  66.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-2-Acetyl-6,7-bis(benzyloxy)-1-<(3,4,5-trimethoxyphenyl)methylene>-1,2,3,4-tetrahydroisoquinoline 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 乙醇 为溶剂， 生成 夜罗宁
  参考文献：
  名称：

  Asymmetric synthesis of isoquinoline alkaloids by homogeneous catalysis

  摘要：

  DOI：

  10.1021/ja00282a054
• 作为产物：
  描述：

  1-(3',4',5'-Trimethoxybenzyl)-6,7-dibenzyloxy-3,4-dihydroisochinolin 、 乙酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (Z)-2-Acetyl-6,7-bis(benzyloxy)-1-<(3,4,5-trimethoxyphenyl)methylene>-1,2,3,4-tetrahydroisoquinoline 、 (E)-2-Acetyl-6,7-bis(benzyloxy)-1-<(3,4,5-trimethoxyphenyl)methylene>-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

• Process for preparing N-acyltetrahydroisoquinoline
  申请人：Takasago Perfumery Co., Ltd.

  公开号：US04851537A1

  公开（公告）日：1989-07-25

  A process for preparing an N-acyltetrahydroisoquinoline represented by formula (II) ##STR1## wherein A represents a phenylene ring substituted with a hydroxyl group, a lower alkoxy group, an acetoxy group, or a benzyloxy group; R represents a hydrogen atom, a lower alkyl group, or a phenyl group; and X represents a hydrogen atoms, a phenyl group, or a phenyl group substituted with a hydroxyl group, a lower alkoxy group, or an acetoxy group, which comprises asymmetrically hydrogenating an N-acyl-1-methylenetetrahydroisoquinoline or N-acyl-1-benzylidenetetrahydroisoquinoline represented by formula (I) ##STR2## wherein A, R, and X are as defined above, in the presence of an optically active ruthenium-phosphine complex as a catalyst. The process exclusively and efficiently provides a useful isomer of the N-acyltetrahydroisoquinoline of high purity which is useful as an intermediate for synthesizing isoquinoline type alkaloids as pharmaceuticals without involving optical resolution of a racemate.

  一种制备式（II）的N-酰基四氢异喹啉的方法，其中A代表取代有羟基、低级烷氧基、乙酰氧基或苄氧基的苯环；R代表氢原子、低级烷基或苯基；X代表氢原子、苯基或取代有羟基、低级烷氧基或乙酰氧基的苯基，包括在手性铑膦配合物催化剂的存在下，对式（I）所代表的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进行不对称氢化，其中A、R和X如上所定义。该方法以高纯度的N-酰基四氢异喹啉的有用异构体为唯一和高效的产物，该异构体可用作合成异喹啉类生物碱药物的中间体，而不涉及拆分外消旋体的光学分辨过程。
• NOYORI, RYOJI;KITAMURA, MASATO;TAKAYA, HIDEMASA;KUMOBAYASHI, HIDENORI;AKU+
  作者：NOYORI, RYOJI、KITAMURA, MASATO、TAKAYA, HIDEMASA、KUMOBAYASHI, HIDENORI、AKU+

  DOI：——

  日期：——
• US4851537A
  申请人：——

  公开号：US4851537A

  公开（公告）日：1989-07-25
• 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
• General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes
  作者：Masato Kitamura、Yi Hsiao、Masako Ohta、Masaki Tsukamoto、Tetsuo Ohta、Hidemasa Takaya、Ryoji Noyori

  DOI：10.1021/jo00081a007

  日期：1994.1

  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.