((S)-1-tert-Butoxymethyl-2-methyl-propyl)-[1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-amine | 128778-92-7

• 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: ((S)-1-tert-Butoxymethyl-2-methyl-propyl)-[1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-amine
• CAS: 128778-92-7
• 化学式: C₂₁H₃₄N₂O₃
• 分子量: 362.513
• InChiKey: BODFJJUURHGGQT-SDLXJUDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.29
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  ((S)-1-tert-Butoxymethyl-2-methyl-propyl)-[1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-amine 在 氨 、 水 、 sodium 、 溶剂黄146 、 叔丁醇 作用下， 反应 3.25h， 生成 (+/-)-2,3-dimethoxy-5,6,8,8a,9,10,13,13a-octahydro-11H-dibenzoquinolizin-1-one
  参考文献：
  名称：

  Asymmetric synthesis of benzoquinolizidines: a formal synthesis of (-)-emetine

  摘要：

  Chiral formamidines affixed to tetrahydroisoquinoline derivatives affords the appropriate precursor 9 to various benzo[a]quinolizidines 2 and 3 and dibenzo[a,g]quinolizidines 4 in modest to high optical purity. Both 3 and 4 have been utilized in total syntheses of natural emetine 1, thus the route herein constitutes a formal total synthesis of 1. Furthermore, Mannich cyclizations of 1-alkylisoquinolines 18a-c proceeded with or without loss of absolute stereochemistry at the C-1 position. Explanation for this behavior is based upon whether a [3,3] rearrangement or a Mannich reaction takes place. The former results in virtually complete racemization of 18, whereas the latter totally conserves the chirality in 18. Finally, 1-alkynylisoquinolines of high optical purity were transformed, via the Overman protocol, to alkylidine benzo[a]quinolizidines 24 in good yield and to our knowledge, high enantiomeric excess.

  DOI：

  10.1021/jo00024a032
• 作为产物：
  描述：

  Valinol-tert-butylether 生成 ((S)-1-tert-Butoxymethyl-2-methyl-propyl)-[1-(6,7-dimethoxy-3,4-dihydro-1H-isoquinolin-2-yl)-meth-(E)-ylidene]-amine
  参考文献：
  名称：

  在不对称合成中使用手性甲form的最新进展

  摘要：

  在手性环境中，在氮旁边生成碳负离子的能力导致了许多有用的不对称途径生成生物碱和相关物质。已经进行了机理研究以了解这些烷基化的性质。

  DOI：

  10.1016/s0040-4020(01)88523-9

文献信息

• (-)-Cryptaustoline: its synthesis, revision of absolute stereochemistry, and mechanism of inversion of stereochemistry
  作者：A. I. Meyers、Thais M. Sielecki、Debbie C. Crans、Robert W. Marshman、Thanh H. Nguyen

  DOI：10.1021/ja00048a020

  日期：1992.10

  The asymmetric synthesis of (S)-(+)-cryptaustoline was accomplished and found to differ in sign of rotation with the natural «S»-(-)-material. The previously assigned absolute configuration was found to be incorrect and is now corrected. The reversal in stereochemistry came about through an unusual manner involving (S)-(+)-laudanosoline (3) cyclizing to (R)-(-)-cryptaustoline ((-)-1c). The mechanism

  完成了 (S)-(+)-cryptaustoline 的不对称合成，发现其旋转符号与天然 «S»-(-)-材料不同。发现先前分配的绝对配置不正确，现在已更正。立体化学的逆转是通过一种不寻常的方式实现的，包括 (S)-(+)-laudanosoline (3) 环化为 (R)-(-)-cryptaustoline ((-)-1c)。通过氧化一系列月桂醇油碱的氘代衍生物来探索该机制，所有这些衍生物都在所得的隐孢子碱中保留了氘
• Catalytic iron-mediated enediene carbocyclizations: The enantioselective synthesis of a homologue of the alkaloid (−)-protoemetinol
  作者：James M. Takacs、Scott C. Boito

  DOI：10.1016/0040-4039(95)00443-g

  日期：1995.4

  The efficient enantioselective synthesis of the benzoquinolizidine 2 highlights the utility of the stereoselective iron-catalyzed cyclization of enedienes and affords the opportunity to prepare analogues of protoemetinol, psychotrine, and related natural products.

  苯并喹喔啉2的有效对映选择性合成突出了立体选择性铁催化烯二烯的环化的实用性，并提供了制备原美托诺尔，精神碱和相关天然产物类似物的机会。
• GOTTLIEB, LEVI;MEYERS, A. I., J. ORG. CHEM., 55,(1990) N1, C. 5659-5662
  作者：GOTTLIEB, LEVI、MEYERS, A. I.

  DOI：——

  日期：——