(8S,10S,14S)-1-azatetracyclo[6.5.1.02,7.010,14]tetradeca-2,4,6-trien-13-one | 145291-74-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (8S,10S,14S)-1-azatetracyclo[6.5.1.02,7.010,14]tetradeca-2,4,6-trien-13-one
• CAS: 145291-74-3
• 化学式: C₁₃H₁₃NO
• 分子量: 199.252
• InChiKey: DWBDDSVOTPZOKE-FWDPORAESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (8S,10S,14S)-1-azatetracyclo[6.5.1.02,7.010,14]tetradeca-2,4,6-trien-13-one 在 硫酸 作用下， 生成 ethyl 3-[(2S,2aS,7bS)-3-acetyl-1,2,2a,7b-tetrahydrocyclobuta[b]indol-2-yl]propanoate
  参考文献：
  名称：

  Intramolecular photochemical cycloadditions of N-alkenyloxycarbonylindoles and N-alkenoylindoles

  摘要：

  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。

  DOI：

  10.1039/c39920001491
• 作为产物：
  描述：

  1-(1H-indol-1-yl)pent-4-en-1-one 以 苯 为溶剂， 以92%的产率得到(8S,10S,14S)-1-azatetracyclo[6.5.1.02,7.010,14]tetradeca-2,4,6-trien-13-one
  参考文献：
  名称：

  Intramolecular photochemical cycloadditions of N-alkenyloxycarbonylindoles and N-alkenoylindoles

  摘要：

  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。

  DOI：

  10.1039/c39920001491

文献信息

• 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。
• Intramolecular Photochemical Cycloaddition Reactions of N-[(.omega.-Alkenyloxy)carbonyl]indoles and N-(.omega.-Alkenoyl)indoles
  作者：David L. Oldroyd、Alan C. Weedon

  DOI：10.1021/jo00085a022

  日期：1994.3

  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.
• Photocatalytic Intramolecular [2 + 2] Cycloaddition of Indole Derivatives via Energy Transfer: A Method for Late-Stage Skeletal Transformation
  作者：Zhijie Zhang、Dong Yi、Min Zhang、Jun Wei、Ji Lu、Lin Yang、Jun Wang、Na Hao、Xianchao Pan、Shiqi Zhang、Siping Wei、Qiang Fu

  DOI：10.1021/acscatal.0c01841

  日期：2020.9.4

  cycloaddition of indole derivatives tethered with olefins at the N1 position has been considered thermodynamically unfeasible due to the high triplet excited-state energies. We describe visible light-promoted [2 + 2] cycloaddition with concomitant dearomatization of indole derivatives tethered with olefins at the N1 position via the energy transfer process, providing cyclobutane-fused polycyclic indoline derivatives

  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。