Methyl 1-(3-methyl-3-buten-1-yl)indole-3-carboxylate

• 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: Methyl 1-(3-methyl-3-buten-1-yl)indole-3-carboxylate
• 英文别名: methyl 1-(3-methylbut-3-en-1-yl)-1H-indole-3-carboxylate；Methyl 1-(3-methylbut-3-enyl)indole-3-carboxylate
• 化学式: C₁₅H₁₇NO₂
• 分子量: 243.305
• InChiKey: CSFKXHQWLSHMIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Methyl 1-(3-methyl-3-buten-1-yl)indole-3-carboxylate 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 16.0h， 以100%的产率得到1-(3-methylbut-3-en-1-yl)-1H-indole-3-carboxylic acid
  参考文献：
  名称：

  铑(III)催化的分子内氢化芳基化、酰胺芳基化和Heck型反应：由酰胺导向基团确定的三种不同途径

  摘要：

  酰胺决定：通过改变酰胺导向基团，可以实现多种束缚烯烃的三种不同的铑(III)催化反应途径。这为生产无数复杂的多环产物提供了一条有效的途径，其中许多含有新形成的全碳四元中心。酰胺芳基化可以非对映选择性地提供具有多达三个连续立体中心的产物。

  DOI：

  10.1002/anie.201307631
• 作为产物：
  描述：

  吲哚-3-甲酸甲酯 在 三甲基氯硅烷 、 四丁基氢氧化铵 、 双氧水 、 iron(II) sulfate 、 sodium iodide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二甲基亚砜 、 乙腈 为溶剂， 反应 14.0h， 生成 Methyl 1-(3-methyl-3-buten-1-yl)indole-3-carboxylate
  参考文献：
  名称：

  Oxidative Radical Cyclization of (.omega.-Iodoalkyl)indoles and Pyrroles. Synthesis of (-)-Monomorine and Three Diastereomers

  摘要：

  Addition of excess hydrogen peroxide (10 equiv) to a sonicated solution of FeSO4:7H(2)O (1 equiv) in Dh ISO containing the N-(omega-iodoalkyl)indoles 4, 5, 11, and 13 effected oxidative radical cyclization to 6, 7, 14, and 15, respectively. The (omega-iodoalkyl)pyrroles 21, 22, 27, 38, and 49 underwent analogous cyclization reactions to 23, 24, 28, 39, and 50, respectively. The regiochemistry of these radical cyclization reactions was correctly predicted by FMO calculations in all cases but one. For compound 38, FMO calculations indicated that radical attack should take place at both C-3 and C-5. Only the product of cyclization at C-5, i.e., 39, was observed. The enantiomerically pure bicyclic ketone 42, prepared by the above technique from the iodide 53, was converted into 55 which, on catalytic reduction (H-2/Rh-A1(2)O(3)), gave a mixture of (-)-monomorine (40) and three of its diastereomers 56-58 (see, however, Note Added in Proof).

  DOI：

  10.1021/jo00088a029

文献信息

• Palladium-Catalyzed Intermolecular Polarity-Mismatched Addition of Unactivated Alkyl Radicals to Unactivated Alkenes
  作者：Xiaojin Wu、Guanlin Xiao、Yalan Ding、Ying Zhan、Yao Zhao、Rizhi Chen、Teck-Peng Loh

  DOI：10.1021/acscatal.0c04013

  日期：2020.12.4

  A palladium-catalyzed intermolecular polarity-mismatched addition of unactivated alkyl radicals to unactivated alkenes was developed for the first time. In the two-component dicarbofunctionalization, a variety of primary, secondary, and tertiary unactivated alkyl halides regioselectively reacted with various unactivated olefins. A series of structurally complex heteropolycycles decorated with a quaternary

  首次开发了钯催化的分子间极性不匹配的未活化烷基与未活化烯烃的加成反应。在双组分双碳官能化中，各种伯，仲和叔未活化的烷基卤与各种未活化的烯烃区域选择性地反应。已经有效地合成了一系列装饰有季碳中心的结构复杂的杂多环。
• Iron-Mediated Hydrogen Atom Transfer Radical Cyclization of Alkenyl Indoles and Pyrroles Gives Their Fused Derivatives: Total Synthesis of Bruceolline E and H
  作者：Santosh J. Gharpure、Rupali S. Chavan、Simran R. Narang

  DOI：10.1021/acs.orglett.4c00032

  日期：——

  employed for the synthesis of dihydropyrroloindoles and dihydropyrrolizines via 5-exo-trig radical cyclization where indoles and pyrroles are used as an acceptor. This radical approach has also been extended for the synthesis of tetrahydrocyclopenta[b]indolones via the Baldwin-disfavored 5-endo-trig cyclization pathway. The formal synthesis of bruceolline J and the total synthesis of bruceollines E

  铁介导的氢原子转移（HAT）反应可有效地用于通过 5- exo - trig自由基环化合成二氢吡咯并吲哚和二氢吡咯嗪，其中吲哚和吡咯用作受体。这种激进的方法还被扩展到通过鲍德温不喜欢的 5- end - trig环化途径合成四氢环戊[ b ]吲哚酮。采用前一种策略，布鲁斯酚J的正式合成以及布鲁斯酚E和H的全合成都已顺利进行。
• Oxidative Radical Cyclization of (.omega.-Iodoalkyl)indoles and Pyrroles. Synthesis of (-)-Monomorine and Three Diastereomers
  作者：Dean R. Artis、In-Seop Cho、Saul Jaime-Figueroa、Joseph M. Muchowski

  DOI：10.1021/jo00088a029

  日期：1994.5

  Addition of excess hydrogen peroxide (10 equiv) to a sonicated solution of FeSO4:7H(2)O (1 equiv) in Dh ISO containing the N-(omega-iodoalkyl)indoles 4, 5, 11, and 13 effected oxidative radical cyclization to 6, 7, 14, and 15, respectively. The (omega-iodoalkyl)pyrroles 21, 22, 27, 38, and 49 underwent analogous cyclization reactions to 23, 24, 28, 39, and 50, respectively. The regiochemistry of these radical cyclization reactions was correctly predicted by FMO calculations in all cases but one. For compound 38, FMO calculations indicated that radical attack should take place at both C-3 and C-5. Only the product of cyclization at C-5, i.e., 39, was observed. The enantiomerically pure bicyclic ketone 42, prepared by the above technique from the iodide 53, was converted into 55 which, on catalytic reduction (H-2/Rh-A1(2)O(3)), gave a mixture of (-)-monomorine (40) and three of its diastereomers 56-58 (see, however, Note Added in Proof).
• Rhodium(III)-Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck-type Reaction: Three Distinct Pathways Determined by an Amide Directing Group
  作者：Tyler A. Davis、Todd K. Hyster、Tomislav Rovis

  DOI：10.1002/anie.201307631

  日期：2013.12.23

  reaction pathways of a wide variety of tethered alkenes can be accessed through changing the amide directing group. This provides an efficient route to a myriad of complex polycyclic products, many containing newly formed all‐carbon quaternary centers. Amidoarylations can diastereoselectively deliver products with up to three contiguous stereocenters.

  酰胺决定：通过改变酰胺导向基团，可以实现多种束缚烯烃的三种不同的铑(III)催化反应途径。这为生产无数复杂的多环产物提供了一条有效的途径，其中许多含有新形成的全碳四元中心。酰胺芳基化可以非对映选择性地提供具有多达三个连续立体中心的产物。