1,2,3,9-tetrahydro-3-methyl-4H-carbazol-4-one | 129483-26-7

• 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: 1,2,3,9-tetrahydro-3-methyl-4H-carbazol-4-one
• 英文别名: 3-Methyl-1,2,3,9-tetrahydro-4H-carbazol-4-one；3-methyl-2,3-dihydro-1H-carbazol-4(9H)-one；3-methyl-1,2,3,4-tetrahydro-9H-carbazole-4-one；3-Methyl-1,2,3,9-tetrahydrocarbazol-4-one
• CAS: 129483-26-7
• 化学式: C₁₃H₁₃NO
• 分子量: 199.252
• InChiKey: PSQCRFSOCVLYJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  32.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2,3,9-tetrahydro-3-methyl-4H-carbazol-4-one 在 palladium on activated charcoal 二苯醚 、 1,2,4-三甲基苯 作用下， 以 二苯醚 为溶剂， 反应 20.0h， 以63%的产率得到4-hydroxy-3-methyl-9H-carbazole
  参考文献：
  名称：

  Palladium-catalyzed synthesis of 1,2-dihydro-4(3H)-carbazolones. Formal total synthesis of murrayaquinone A

  摘要：

  Two sequential palladium-catalyzed reactions are the key steps in a novel synthetic route to 1,2-dihydro-4(3H)-carbazolones. The steps are an intermolecular Stille cross-coupling followed by a reductive N-heteroannulation. A formal total synthesis of murrayaquinone A, employing this sequence, is reported. (C) 2003 Elsevier Ltd. All fights reserved.

  DOI：

  10.1016/s0040-4020(03)00976-1
• 作为产物：
  描述：

  3-甲基-2,3,4,9-四氢-1H-咔唑 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 1,2,3,9-tetrahydro-3-methyl-4H-carbazol-4-one
  参考文献：
  名称：

  振动光谱和质谱联用检测和表征氧代环己烷[b]吲哚

  摘要：

  一组具有代表性的九种氧代环己烷[ b ]吲哚（具有 6,5,6 环模式的三环吲哚）的振动和质谱，其中第三个非芳香环的四个位置和最多两个位置上都有一个羰基报告并讨论了连接到该环其他位置的碳原子上的甲基取代基。特别关注的是使用红外光谱来确定这些化合物是否可以最好地描述为酮吲哚或羟基吲哚。大多数这些光谱表明三环杂环优先存在于酮吲哚上，但氧代环己烷的固态红外光谱[ b] 4 位带有氧官能团的吲哚非常不寻常，给人的第一印象是这些化合物是羟基吲哚。计算模型支持这样的解释：4-酮吲哚互变异构体的能量低于其最稳定的异构吲哚构象异构体。质谱分析法为区分异构电离氧代环己烷[ b ]吲哚提供了有价值的确证证据，该异构体离子化氧代环己烷[ b ]吲哚通过独特且信息丰富的裂解途径解离，其中中间双子离子的稳定性似乎受到孤对电子参与的深刻影响氮原子上。许多这些碎片可以通过逐步机制更好地描述，而不是作为协调的环回复。

  DOI：

  10.1016/j.molstruc.2023.136311

文献信息

• Hypervalent Iodine(III)‐Mediated Counteranion Controlled Intramolecular Annulation of Exocyclic β‐Enaminone to Carbazolone and Imidazo[1,2‐<i>a</i>]pyridine Synthesis
  作者：Dhananjay Bhattacherjee、Shankar Ram、Arvind Singh Chauhan、Yamini、Sheetal、Pralay Das

  DOI：10.1002/chem.201806299

  日期：2019.4.23

  A highly efficient and flexible protocol for intramolecular annulation of exocyclic β‐enaminones has been disclosed for the synthesis of carbazolones and imidazo[1,2‐a]pyridines through a counter‐anion‐controlled free‐radical mechanism promoted by hypervalent iodine(III). The cooperative behavior of HTIB and AgSbF6 plays a crucial role in the intramolecular annulation process through C−C and C−N bond

  为环外β-烯胺酮的分子内环化一个高效和灵活的协议已经公开了carbazolones和咪唑并[1,2的合成一个]吡啶通过高价碘促进的抗衡阴离子控制自由基机理（III） 。HTIB和AgSbF 6的协同行为在通过CC和CN键形成所需的分子内环化过程中起着至关重要的作用。机械学的见解表明，系统中涉及的两个竞争性反应是由抗衡阴离子的性质决定的，抗衡阴离子的性质决定了最终产物的形成。制备并分离了各种咔唑酮和咪唑并[1,2- a ]吡啶分子，收率良好至极佳。
• A new strategy for the enantioselective synthesis of aspidosperma alkaloids: I - Construction of the [ABC]-type tricyclic intermediates.
  作者：Jean d'Angelo、Didier Desmaele

  DOI：10.1016/s0040-4039(00)94653-7

  日期：1990.1

  Carbazolone19has been prepared in eight steps from cyclohexanone11(36% overall yield).

  Carbazolone 19已经在从环己酮八个步骤制备11 （36％总收率）。
• Divergent Coupling of 2-Carbonyl-anilines and Diazo-cyclopentanones: Asymmetric Total Synthesis of (+)-Leucomidine A
  作者：Xiaotong Yao、Xiaosong Shan、Liansuo Zu

  DOI：10.1021/acs.orglett.8b02823

  日期：2018.10.19

  The direct coupling of 2-carbonyl-anilines and diazo-cyclopentanones, promoted by a rhodium catalyst and diphenyl phosphate, is reported for the divergent generation of both carbazolones and indolones. The strategy allows for the successful transfer of the substituents/functionality and the chirality of the coupling partners into the functionalized heterocyclic products, thus serving as the strategic

  据报道，铑催化剂和磷酸二苯酯促进了2-羰基苯胺和重氮-环戊酮的直接偶联，从而产生了咔唑酮和吲哚酮。该策略可以将取代基/官能团和偶联伙伴的手性成功转移到官能化的杂环产物中，从而可以作为天然产物合成的战略基础，如（+）-隐香氨酸A的简明不对称全合成所证明的那样。 。
• Gulle, Sibel; Ergun, Yavuz, Asian Journal of Chemistry, 2010, vol. 22, # 7, p. 5517 - 5522
  作者：Gulle, Sibel、Ergun, Yavuz

  DOI：——

  日期：——
• Stereocontrolled Elaboration of Quaternary Carbon Centers through the Asymmetric Michael Reaction Using Chiral Imines: Enantioselective Synthesis of (+)-Aspidospermidine
  作者：Didier Desmaeele、Jean d'Angelo

  DOI：10.1021/jo00088a008

  日期：1994.5

  An enantioselective synthesis of (+)-aspidospermidine (1b) has been developed. The key strategic element was the stereocontrolled elaboration of quaternary carbon centers through the asymmetric Michael reaction, using chiral imines under neutral conditions. Thus, addition of imine 21, prepared from 2-ethylcyclohexanone and (R)-1-phenylethylamine, to methyl acrylate, led to cyclohexanone (S)-20 with 90% stereoselectivity (Scheme 3). The latter compound was then converted in six steps into dione 19 (Chart 6). Synthesis of [ABC]-type tricyclic carbazolone 18 was next accomplished, starting from this dione, by using the indole synthesis protocol developed by Suzuki. Critical to the success of this approach was the evolution, after extensive experimentation, of an efficient sequence for assembling D ring to carbazolone 18, having controlled during the events the ''natural'', cis CD ring junction. Thus, treatment of alcohol 57 with trifluoroacetic acid led to tetracycle 58 obtained as a single isomer with 94% yield (Chart 10). The intramolecular capture of a putative intermediary iminium ion, as illustrated in 52, by the carbamate nitrogen atom of 57 has been evoked to rationalize the observed stereoselectivity. The strategy we have adopted for the construction of the fifth E ring of 1b was in fact the methodology proposed by Magnus, based on an intramolecular Pummerer rearrangement (17 --> 59). Thus, synthesis of (+)-aspidospermidine (1b) has been achieved by a linear sequence of 22 chemical operations, starting with 2-ethylcyclohexanone, with an overall yield of 2.7%.