2-Benzoyl-1-<(3,4-dimethoxyphenyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline | 97157-25-0

• 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: 2-Benzoyl-1-<(3,4-dimethoxyphenyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: 2-benzoyl-1-(3,4-dimethoxy-benzyl)-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline；2-benzoyl-6,7-dimethoxy-1-veratryl-1,2,3,4-tetrahydro-isoquinoline；2-Benzoyl-6,7-dimethoxy-1-veratryl-1,2,3,4-tetrahydro-isochinolin；[1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl]-phenylmethanone
• CAS: 97157-25-0
• 化学式: C₂₇H₂₉NO₅
• 分子量: 447.531
• InChiKey: UGFRSKYDRZKRON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Benzoyl-1-<(3,4-dimethoxyphenyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 在 氢氧化钾 、 一水合肼 作用下， 以 乙二醇 为溶剂， 反应 17.0h， 以47%的产率得到S-四氢罂粟碱
  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：

  1,2,3,4-tetrahydro-6,7-dimethoxy-2-(3,4-dimethoxybenzyl)isoquinoline 在 氯仿 作用下， 生成 2-Benzoyl-1-<(3,4-dimethoxyphenyl)methyl>-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  CLXXXII.—异喹啉衍生物。第二部分 罂粟碱还原产物的组成

  摘要：

  DOI：

  10.1039/ct9099501610

文献信息

• NOYORI, RYOJI;KITAMURA, MASATO;TAKAYA, HIDEMASA;KUMOBAYASHI, HIDENORI;AKU+
  作者：NOYORI, RYOJI、KITAMURA, MASATO、TAKAYA, HIDEMASA、KUMOBAYASHI, HIDENORI、AKU+

  DOI：——

  日期：——
• CLXXXII.—isoQuinoline derivatives. Part II. The constitution of the reduction products of papaverine
  作者：Frank Lee Pyman

  DOI：10.1039/ct9099501610

  日期：——
• 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.