ethyl 3,4-dichloro-1,6-dicyano-2,5-dioxo-8-(4,5,6,7-tetrahydro-1H-indol-2-yl)bicyclo[4.2.0]octa-3,7-diene-7-carboxylate | 1220987-17-6

• 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: ethyl 3,4-dichloro-1,6-dicyano-2,5-dioxo-8-(4,5,6,7-tetrahydro-1H-indol-2-yl)bicyclo[4.2.0]octa-3,7-diene-7-carboxylate
• CAS: 1220987-17-6
• 化学式: C₂₁H₁₅Cl₂N₃O₄
• 分子量: 444.274
• InChiKey: HCMJEJPJDWYJKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  124
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3,4-dichloro-1,6-dicyano-2,5-dioxo-8-(4,5,6,7-tetrahydro-1H-indol-2-yl)bicyclo[4.2.0]octa-3,7-diene-7-carboxylate 在 水 作用下， 以 叔丁醇 为溶剂， 反应 2.0h， 以24%的产率得到ethyl 3,4-dicyano-4-(3,4-dichloro-2-hydroxy-5-oxo-2,5-dihydrofuran-2-yl)-2-(4,5,6,7-tetrahydroindol-2-yl)cyclobut-1-enecaboxylate
  参考文献：
  名称：

  From 4,5,6,7-tetrahydroindole to functionalized furan-2-one–4,5,6,7-tetrahydroindole–cyclobutene sequence in two steps

  摘要：

  Ethyl 3-(4,5,6,7-tetrahydroindol-2-yl)propynoate, readily available from 4,5,6,7-tetrahydroindole and ethyl bromopropynoate, when treated with dichlorodicyanobenzoquinone (DDQ) in methanol affords furan-2-one-4,5,6,7-tetrahydroindole-cyclobutene sequence in a 52% yield. As kinetic and minor products, a furan-2-one isomer along with bicycloheptadienone have been either isolated or identified. The reaction has been shown to proceed via the isolable intermediate the [2+2]-cycloadduct of ethyl 3-(4,5,6,7-tetrahydroindo1-2-yl)propynoate with DDQ. Other alcohols react with the [2+2]-cycloadduct in a similar way. The effect of the alcohol structure on the products ratio has been analyzed. All the intermediates and products are formed as single diastereomer, thus indicating a concerted character of the rearrangement. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.018
• 作为产物：
  描述：

  4,5,6,7-四氢吲哚 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 ethyl 3,4-dichloro-1,6-dicyano-2,5-dioxo-8-(4,5,6,7-tetrahydro-1H-indol-2-yl)bicyclo[4.2.0]octa-3,7-diene-7-carboxylate
  参考文献：
  名称：

  From 4,5,6,7-tetrahydroindole to functionalized furan-2-one–4,5,6,7-tetrahydroindole–cyclobutene sequence in two steps

  摘要：

  Ethyl 3-(4,5,6,7-tetrahydroindol-2-yl)propynoate, readily available from 4,5,6,7-tetrahydroindole and ethyl bromopropynoate, when treated with dichlorodicyanobenzoquinone (DDQ) in methanol affords furan-2-one-4,5,6,7-tetrahydroindole-cyclobutene sequence in a 52% yield. As kinetic and minor products, a furan-2-one isomer along with bicycloheptadienone have been either isolated or identified. The reaction has been shown to proceed via the isolable intermediate the [2+2]-cycloadduct of ethyl 3-(4,5,6,7-tetrahydroindo1-2-yl)propynoate with DDQ. Other alcohols react with the [2+2]-cycloadduct in a similar way. The effect of the alcohol structure on the products ratio has been analyzed. All the intermediates and products are formed as single diastereomer, thus indicating a concerted character of the rearrangement. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.018

文献信息

• Facile [2+2] Cycloaddition of DDQ to an Alkyne: Synthesis of Pyrrolyl- and Indolylbicyclo[4.2.0]octadienes from C-Ethynylpyrroles or C-Ethynylindoles
  作者：Boris Trofimov、Lyubov’ Sobenina、Zinaida Stepanova、Igor’ Ushakov、Lidiya Sinegovskaya、Tamara Vakul’skaya、Al’bina Mikhaleva

  DOI：10.1055/s-0029-1217133

  日期：2010.2

  C-Ethynylpyrroles or -indoles, which can be prepared by cross-coupling of pyrroles or indoles with haloalkynes on active surfaces, undergo [2+2]-cycloaddition reactions with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to give 2-pyrrolyl- or 3-indolylbicyclooctadienes in almost quantitative yields. The adducts are charge-transfer complexes that are paramagnetic in the solid state, and therefore represent a new family of densely functionalized pyrrole and indole derivatives potentially useful as pharmaceutical candidates, highly potent building blocks, or precursors of advanced materials. The reaction contributes to the practical and basic chemistry of pyrroles, indoles, alkynes, and quinones.

  C-乙炔基吡咯或吲哚，可通过吡咯或吲哚与卤代炔烃在活性表面上进行交叉耦合制备，与2,3-二氯-5,6-二氰基-1,4-苯醌发生[2+2]环加成反应，以几乎定量的产率生成2-吡咯基或3-吲哚基双环辛二烯。这些加成物是固态下顺磁性的电荷转移复合物，因此代表了一类新型的密集功能化吡咯和吲哚衍生物，可能作为潜在的药物候选者、高效构建模块或高级材料的前体。该反应促进了吡咯、吲哚、炔烃和醌的实用及基础化学研究。
• Rearrangements of the [2+2]-cycloadducts of DDQ and 2-ethynylpyrroles
  作者：Boris A. Trofimov、Lyubov N. Sobenina、Zinaida V. Stepanova、Igor A. Ushakov、Albina I. Mikhaleva、Denis N. Tomilin、Olga N. Kazheva、Grigorii G. Alexandrov、Anatolii N. Chekhlov、Oleg A. Dyachenko

  DOI：10.1016/j.tetlet.2010.07.100

  日期：2010.9

  2-ethynylpyrroles, upon ethanolysis (reflux, 15 min or room temperature, 24 h), rearrange from bicyclo[4.2.0]octadienediones to bicyclo[3.2.0]heptadienone- and cyclobutenyl-dihydrofuranone moieties in 55–83% yields, the former rearrangement being the major direction. Benzoquinone ring cleavage is regioselective to afford mostly bicyclo[3.2.0]heptadienone-pyrrole ensembles (85–90% selectivity) in 39–78% yields. The

  DDQ和2-乙炔基吡咯的[2 + 2]-环加合物在乙醇分解（回流，15分钟或室温，24小时）后，从双环[4.2.0]十八二烯基重排为双环[3.2.0]庚二烯酮和环丁烯基-二氢呋喃酮部分的产率为55-83％，前者的重排是主要方向。苯醌醌环的裂解具有区域选择性，以39-78％的收率提供大部分双环[3.2.0]庚二烯酮-吡咯团（选择性85-90％）。唯一的例外是当起始化合物包含乙氧羰基取代基且吡咯对应物为4,5,6,7-四氢吲哚片段时。在这种情况下，重排产物的比例为1：1.2，总产率为83％。二氢呋喃酮途径重排的重要特征是其100％非对映选择性。