1-Indol-1-yl-hex-5-en-1-one | 145291-78-7

• 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: 1-Indol-1-yl-hex-5-en-1-one
• 英文别名: 1-Indol-1-ylhex-5-en-1-one
• CAS: 145291-78-7
• 化学式: C₁₄H₁₅NO
• 分子量: 213.279
• InChiKey: UDEPNMUIGUNSBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 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：
  22
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Indol-1-yl-hex-5-en-1-one 在 2,2,2-三氟乙醇 、 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 作用下， 反应 12.0h， 以65%的产率得到(8S,10S,15S)-1-azatetracyclo[6.6.1.02,7.010,15]pentadeca-2,4,6-trien-14-one
  参考文献：
  名称：

  通过能量转移的吲哚衍生物的光催化分子内[2 + 2]环加成：一种晚期骨骼转化的方法

  摘要：

  由于高三重态激发态能量，在N1位置与烯烃拴在一起的吲哚衍生物的可见光促进脱芳香性[2 + 2]环加成反应在热力学上不可行。我们描述了可见光促进的[2 + 2]环加成反应，以及通过能量转移过程在N1位置与烯烃拴在一起的吲哚衍生物的脱芳香化，同时提供了可用于药物设计和发现的环丁烷稠合多环吲哚啉衍生物。这些环丁烷稠合的基于二氢吲哚的多环化合物以高收率和良好的非对映选择性（> 99：1）获得。反应成功的关键是在氮之间形成氢键-链烯基吲哚和溶剂，能够降低吲哚衍生物的三重态能量，从而大大提高了方案的效率。含吲哚生物活性分子的后期骨骼多样化证明了该方法的适用性，这为快速骨架重塑提供了强有力的策略。DFT计算用于深入了解反应途径。

  DOI：

  10.1021/acscatal.0c01841
• 作为产物：
  描述：

  吲哚 、 5-己酰氯 在 sodium hydroxide 、 四丁基溴化铵 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以40%的产率得到1-Indol-1-yl-hex-5-en-1-one
  参考文献：
  名称：

  Intramolecular Photochemical Cycloaddition Reactions of N-[(.omega.-Alkenyloxy)carbonyl]indoles and N-(.omega.-Alkenoyl)indoles

  摘要：

  Ultraviolet light irradiation of N-(but-3'-enoyl)indole (3i), N-(pent-4'-enoyl)indole (3j), and N-(hex-5'-enoyl) indole (3k) affords intramolecular photocycloadducts 17a-19a in which the termini of the side-chain alkene have become bonded to the 2- and 3-positions of the indole ring. The regiochemistry of the addition of the alkene is the opposite to that obtained in the corresponding intermolecular reaction of an N-acylindole with a monosubstituted alkene. The length of the methylene linkage between the tethered alkene and the N-acyl activating group in these N-alkenoylindoles affects the quantum efficiency of intramolecular cycloaddition as well as the ability of the reaction to compete with intermolecular cycloaddition in the presence of added cyclopentene. In contrast, the N-(omega-alkenyloxycarbonyl)indoles 3a-e are relatively photostable, apparently because they are frozen in an unreactive conformation for the duration of the excited state lifetime. Compounds 3a-e are, however, capable of undergoing intermolecular photocycloaddition in the presence of added alkenes and they also photodimerize. These reaction pathways dominate when lower energy wavelengths (lambda>300 nm) of ultraviolet light are used; irradiations performed at higher, energy wavelength (254 nm) give predominantly photo-Fries rearrangement products.

  DOI：

  10.1021/jo00085a022

文献信息

• Indole and Pyrrole Derivatives as Pre-photocatalysts and Substrates in the Sulfonyl Radical-Triggered Relay Cyclization Leading to Sulfonylated Heterocycles
  作者：Ran Yang、Dong Yi、Kunrong Shen、Qiang Fu、Jun Wei、Ji Lu、Lin Yang、Li Wang、Siping Wei、Zhijie Zhang

  DOI：10.1021/acs.orglett.2c00472

  日期：2022.3.18

  A visible-light-induced method for the construction of heterocyclic scaffolds such as pyrido[1,2-a]indoles and indolizines via sulfonyl radical-triggered relay cyclization without employing any external photocatalyst has been developed. Preliminary mechanistic investigation indicated that indole and pyrrole derivatives could serve as pre-photocatalysts to promote the sulfonylation/cyclization, thereby

  已经开发了一种可见光诱导的方法，用于在不使用任何外部光催化剂的情况下通过磺酰基自由基触发的中继环化构建吡啶并[1,2 - a ]吲哚和中氮茚等杂环支架。初步机理研究表明，吲哚和吡咯衍生物可以作为预光催化剂促进磺酰化/环化，从而为合成有价值的磺酰化杂环提供了一种简便的方法。
• Intramolecular photochemical cycloadditions of N-alkenyloxycarbonylindoles and N-alkenoylindoles
  作者：David L. Oldroyd、Alan C. Weedon

  DOI：10.1039/c39920001491

  日期：——

  Ultraviolet light irradiation of N-alkenoylindoles affords intramolecular [2 + 2] photocycloadducts with regiochemistry opposite to that obtained in the corresponding intermolecular reaction; in contrast, N-alkenyloxycarbonylindoles appear to be relatively photostable because they are frozen in an unreactive conformation for the duration of the excited state lifetime.

  N-烯酰基吲哚的紫外光照射可形成具有与相应的分子间反应相反的区域化学性质的分子内[2 + 2]光环加成产物；相比之下，N-烯基氧羧基吲哚似乎相对光稳定，因为它们在激发态寿命内保持在一个不活泼的构象中。
• Visible-light-induced radical cascade cyclization: a catalyst-free synthetic approach to trifluoromethylated heterocycles
  作者：Chuan Yang、Wei Shi、Jian Tian、Lin Guo、Yating Zhao、Wujiong Xia

  DOI：10.3762/bjoc.20.12

  日期：——

  Abstract A visible-light-promoted research protocol for constructing dihydropyrido[1,2-a]indolone skeletons is herein described proceeding through a cascade cyclization mediated by trifluoromethyl radicals. This method allows the efficient synthesis of various indole derivatives without the need of photocatalysts or transition-metal catalysts. Mechanism experiments indicate that the process involves

  抽象 本文描述了一种用于构建二氢吡啶[1,2-a]吲哚酮骨架的可见光促进研究方案，该方案通过三氟甲基自由基介导的级联环化进行。该方法允许高效合成各种吲哚衍生物，而无需光催化剂或过渡金属催化剂。机制实验表明，该过程涉及由 Umemoto 试剂的均解引发的自由基链过程。这种简单的方法可以快速获得含有三氟甲基的杂环。 Beilstein J. Org. Chem. 2024, 20, 118–124. doi:10.3762/bjoc.20.12