3-(cyanomethoxycarbonylmethyl)indole-1-carboxylic acid methyl ester | 55747-24-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 3-(cyanomethoxycarbonylmethyl)indole-1-carboxylic acid methyl ester
• 英文别名: 3-(cyano-methoxycarbonyl-methyl)-indole-1-carboxylic acid methyl ester；2-cyano-2-(1-methoxycarbonyl-indol-3-yl)-acetic acid methyl ester；Methyl 3-(1-cyano-2-methoxy-2-oxoethyl)indole-1-carboxylate
• CAS: 55747-24-5
• 化学式: C₁₄H₁₂N₂O₄
• 分子量: 272.26
• InChiKey: IZSKQZQZBOJASR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  81.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(cyanomethoxycarbonylmethyl)indole-1-carboxylic acid methyl ester 在 水 、 sodium hydride 、 sodium hydroxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.75h， 生成 2-氰基-2-吲哚-3-基-丙酸
  参考文献：
  名称：

  2-Cyano-2-indolylpropanoic acid as a chiral derivatizing agent for the absolute configuration assignment of secondary alcohols and primary amines by 1 H NMR and VCD

  摘要：

  A convenient approach for the absolute configuration assignment of secondary alcohols in the (8R,1'R,2'S,5'R)-15,25, (8S,1'R,2'S,5'R)-15,25, (8R,1'R)-21-24, and (8S,l'R)-21-24 ester series, and of primary amines in the (8R,1'R)-32-37 and (8S,1'R)-32-37 amide series, by means of H-1 NMR and VCD spectroscopy, using 2-cyano-2-indolylpropanoic acid as a chiral derivatizing agent is presented. DFT calculations were carried out to demonstrate the anisotropic effect of the indole skeleton on the chiral alcohol or the amine fragment. Vibrational circular dichroism (VCD) measurements of the above series indicated a VCD bisignated couplet resulting from the interaction of the ester carbonyl group and the -CN group. The absolute configuration assignments were further tested by X-ray diffraction analysis. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.04.011
• 作为产物：
  描述：

  吲哚-3-乙腈 以92%的产率得到
  参考文献：
  名称：

  ROZHKOV V. S.; SMUSHKEVICH YU. I.; CYBOPOB N. N., ZH. ORGAN. XIMII , 1976, 12, HO 5, 1076-1079

  摘要：

  DOI：

文献信息

• Enantioselective Michael Additions to α,β-Unsaturated Imides Catalyzed by a Salen−Al Complex
  作者：Mark S. Taylor、Eric N. Jacobsen

  DOI：10.1021/ja037177o

  日期：2003.9.1

  conjugate addition of di- and trisubstituted nitriles to a wide range of acyclic alkyl- and aryl-substituted α,β-unsaturated imides. This new methodology provides access to multifunctional compounds that previously have not been readily accessible in enantioenriched form. Synthetic applications of these products include the preparation of enantiomerically enriched piperidines, as exemplified by an expedient

  (Salen) 铝配合物 1b 是一种有效的催化剂，用于将二取代和三取代腈与各种无环烷基和芳基取代的 α,β-不饱和酰亚胺共轭加成。这种新方法提供了对以前不容易以对映体富集形式获得的多功能化合物的访问。这些产品的合成应用包括制备富含对映异构体的哌啶，例如 (-)-帕罗西汀的不对称催化合成。
• NMR studies of indoles and theirN-carboalkoxy derivatives
  作者：M. S. Morales-Ríos、P. Joseph-Nathan

  DOI：10.1002/mrc.1260251016

  日期：1987.10

  The 13C NMR assignment of indoles and 5‐methoxyindoles substituted at position 3, and some of their N‐carboalkoxy derivatives, was achieved from one‐ and two‐dimensional NMR experiments. Substituent chemical shifts and 1 J(CH) values were evaluated. The dynamic processes of N‐carboalkoxyindoles and N‐carboalkoxyindoline observed by high‐field 1H NMR show the existence of two preferred rotamers around

  3位取代的吲哚和5-甲氧基吲哚及其一些N-碳烷氧基衍生物的13C NMR归属是通过一维和二维NMR实验实现的。评估了取代基化学位移和 1 J(CH) 值。通过高场 1H NMR 观察到的 N-carboalkoxyindoles 和 N-carboalkoxyindoline 的动态过程表明在氨基甲酸酯 NC( O)OR 键周围存在两个优选的旋转异构体，这被解释为频率/场强依赖性现象。
• Synthèse formelle de la (±)-physostigmine
  作者：Martha S. Morales-Ríos、María A. Bucio、Cirilo García-Martínez、Pedro Joseph-Nathan

  DOI：10.1016/0040-4039(94)88082-4

  日期：1994.8

  The synthesis of 3-cyanomethyl-1,3-dimethyl-5-methoxyindol-2-one 2, a precursor for physostigmine 1, was achieved from ethyl 2-cyano-2-(1-carboethoxy-5-methoxy-3-indolyl)acetate 3a.

  由乙基2-氰基-2-（1-羰基乙氧基-5-甲氧基-3-吲哚基）合成了毒扁豆碱1的前体3-氰基甲基-1,3-二甲基-5-甲氧基吲哚-2-one 2。）醋酸3a。
• Formal synthesis of (±)-physostigmine
  作者：Martha S. Morales-Ríos、María A. Bucio、Pedro Joseph-Nathan

  DOI：10.1016/0040-4020(96)00176-7

  日期：1996.4

  The formal synthesis of the indole alkaloid (±)-physostigmine (1) from (Z)-2-hydroxy-5-methoxyindolenine9 is described. The key step of the synthesis is a novel diasteroselective conjugated addition of a Grignard reagent to 9. The relative stereochemistry of the newly formed contiguous chiral centers is established by X-ray crystallography. The stereocontrolled conjugated addition involves the directing

  与吲哚生物碱（±）-physostigmine（正式合成1）将来自（Ž）-2-羟基-5- methoxyindolenine 9进行说明。合成的关键步骤是将格氏试剂与9进行新颖的非对映选择性共轭加成反应。通过X射线晶体学确定新形成的连续手性中心的相对立体化学。立体控制的共轭加成涉及相邻羟基的引导作用以提供12。氧化12与导致羟吲哚14。后者脱羧，然后进行N-甲基化，得到2,3-二氢-5-甲氧基-1,3-二甲基-2-氧代-1H-吲哚-3-乙腈（3），是毒扁豆碱（1）的已知前体。
• Morales-Rios, Martha S.; Bucio-Vasquez, Ma. Alvina; Joseph-Nathan, Pedro, Journal of Heterocyclic Chemistry, 1993, vol. 30, # 4, p. 953 - 956
  作者：Morales-Rios, Martha S.、Bucio-Vasquez, Ma. Alvina、Joseph-Nathan, Pedro

  DOI：——

  日期：——