(S)-1-<(3,4-Dimethoxyphenyl)methyl>-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline | 57651-56-6

• 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: (S)-1-<(3,4-Dimethoxyphenyl)methyl>-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (S)-(+)-1-(3,4-dimethoxybenzyl)-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline.；(S)-1-[(3,4-Dimethoxyphenyl)methyl]-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline；(1S)-1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxy-3,4-dihydro-1H-isoquinoline-2-carbaldehyde
• CAS: 57651-56-6
• 化学式: C₂₁H₂₅NO₅
• 分子量: 371.433
• InChiKey: UFUAVFDPXUVIHH-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (S)-1-<(3,4-Dimethoxyphenyl)methyl>-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以80%的产率得到(S)-劳丹素
  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：

  3,4-二甲氧基苯乙胺 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 生成 (S)-1-<(3,4-Dimethoxyphenyl)methyl>-2-formyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline
  参考文献：
  名称：

  Synthesis of R-laudanosine and 9-R-O-methylflavinantine by asymmetric alkylation

  摘要：

  DOI：

  10.1016/s0040-4039(00)80079-9

文献信息

• Enantioselective Synthesis of Tetrahydroprotoberberines and Bisbenzylisoquinoline Alkaloids from a Deprotonated α-Aminonitrile
  作者：Nancy Blank、Till Opatz

  DOI：10.1021/jo201871c

  日期：2011.12.2

  for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine, (+)-armepavine, and (+)-laudanosine as well as the tetrahydroprotoberberines (−)-corytenchine and (−)-tetrahydropseudoepiberberine using Noyori’s asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O-methylthalibrine and (+)-tetramethylmagnolamine were obtained from nonracemic

  在受控条件下，可以在α位置对6,7-二甲氧基-1,2,3,4-四氢异喹啉-1-腈进行定量去质子处理。它的烷基化直接提供了3,4-二氢异喹啉，它们可以用作制备各种生物碱的起始原料。在此描述了使用Noyori的不对称转移氢化法制备苄基异喹啉（+）-月桂啶，（+）-阿帕品碱和（+）-月桂碱以及四氢原小ber碱（-）-鸟嘌呤和（-）-四氢伪紫ep碱的方法。在Ullmann二芳基醚合成中，从非外消旋前体获得二聚生物碱（+）- O-甲基thalibrine和（+）-四甲基木酚胺。
• 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