methyl 2-(3-((tert-butoxycarbonyl)oxy)-1-methyl-2-oxo-5-(trifluoromethoxy)indolin-3-yl)acrylate | 1360462-07-2

• 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 2-(3-((tert-butoxycarbonyl)oxy)-1-methyl-2-oxo-5-(trifluoromethoxy)indolin-3-yl)acrylate
• 英文别名: methyl 2-(3-((tertbutoxycarbonyl)oxy)-5-trifluoromethoxy-1-methyl-2-oxoindolin-3-yl)acrylate；Methyl 2-[1-methyl-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-2-oxo-5-(trifluoromethoxy)indol-3-yl]prop-2-enoate；methyl 2-[1-methyl-3-[(2-methylpropan-2-yl)oxycarbonyloxy]-2-oxo-5-(trifluoromethoxy)indol-3-yl]prop-2-enoate
• CAS: 1360462-07-2
• 化学式: C₁₉H₂₀F₃NO₇
• 分子量: 431.366
• InChiKey: YZDXOMMBIIWHEP-UHFFFAOYSA-N

物化性质

• 沸点：
  549.8±50.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  91.4
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  β-硝基苯乙烯 、 methyl 2-(3-((tert-butoxycarbonyl)oxy)-1-methyl-2-oxo-5-(trifluoromethoxy)indolin-3-yl)acrylate 在 α-isocupreine 、 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以63%的产率得到methyl (R)-1′-methyl-2′-oxo-5-phenyl-5′-(trifluoromethoxy)spiro[cyclopenta[2,4]diene-1,3′-indoline]-2-carboxylate
  参考文献：
  名称：

  Tertiary-Amine-Catalyzed Asymmetric [3+2] Annulations of Morita–Baylis–Hillman Carbonates of Isatins with Nitroolefins to Construct Spirooxindoles

  摘要：

  An enantioselective [3+2] annulation of nitroolefins with racemic Morita-Baylis-Hillman carbonates of isatins catalyzed by -isocupreine has been developed. Chiral spirocyclic 2-oxindoles bearing an unusual cyclopentadiene motif were produced in excellent enantioselectivity (up to 98% ee) after the tandem elimination of HNO2 in the presence of DIPEA.

  DOI：

  10.1055/s-0034-1378716

文献信息

• Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins
  作者：Hang Zhang、Shan-Jun Zhang、Qing-Qing Zhou、Lin Dong、Ying-Chun Chen

  DOI：10.3762/bjoc.8.139

  日期：——

  The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita-Baylis-Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee) and in high yields (up to 97%).

  路易斯碱催化源自靛红的 Morita-Baylis-Hillman 碳酸盐的不对称烯丙基胺化提供了一条亲电途径来获得带有 C3-四元立体中心的多功能氧化吲哚，提供良好到出色的对映选择性（高达 94% ee）和高产量（高达 97%）。
• α-Regioselective Asymmetric [3 + 2] Annulations of Morita–Baylis–Hillman Carbonates with Cyclic 1-Azadienes and Mechanism Elucidation
  作者：Kai-Kai Wang、Tian Jin、Xin Huang、Qin Ouyang、Wei Du、Ying-Chun Chen

  DOI：10.1021/acs.orglett.6b00189

  日期：2016.2.19

  An α-regio-, diastereo-, and enantioselective [3 + 2] annulation reaction of Morita–Baylis–Hillman carbonates of isatins and activated alkenes with a bulky electron-withdrawing 1,2-benzoisothiazole 1,1-dioxide or 1,2,3-benzoxathiazine 2,2-dioxide motif is reported, furnishing an array of spirooxindoles (>19:1 dr, up to >99% ee) catalyzed by cinchona-derived tertiary amines. Density functional theory

  Morita-Baylis-Hillman的isatin和活化烯烃碳酸盐与大量吸电子的1,2-苯并异噻唑1,1-二氧化物或1,2的α-区域，非对映和对映选择性[3 + 2]环化反应据报道，由金鸡纳衍生的叔胺催化提供了一系列的螺菌毒素（> 19：1 dr，高达> 99％ee），其中有3-3-苯并恶嗪2，2-二氧化物基序。已经进行了密度泛函理论计算研究，以阐明α-区域选择性环的独创性。
• A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclo[3.1.0]hexane Frameworks
  作者：Zhen‐Hong Yang、Peng Chen、Zhi‐Chao Chen、Zhi Chen、Wei Du、Ying‐Chun Chen

  DOI：10.1002/anie.202102842

  日期：2021.6.14

  species having an activated alkene moiety through a second deprotonation process, which then undergo cascade [1+2]/[3+2] annulations to furnish complex bicyclic [3.1.0]hexane frameworks having three contiguous quaternary stereogenic centers with good to excellent enantioselectivity. Moreover, by using benzoyl aldehyde-derived substrates, a [1+4]/[3+2] annulation sequence is similarly developed to produce

  在这里，我们报告说，在 Morita-Baylis-Hillman 碳酸盐的存在下，可以实现通过去质子化策略对 Tsuji 的 2-（氰甲基）烯丙基碳酸酯进行化学选择性活化以生成钯-三亚甲基甲烷 1,3-偶极子。以下 S N 2'-加成能够通过第二次去质子化过程形成具有活化烯烃部分的新 1,3-偶极物质，然后进行级联 [1+2]/[3+2] 环化以提供复杂的双环[3.1.0] 己烷骨架具有三个连续的四元立体中心，具有良好到出色的对映选择性。此外，通过使用苯甲醛衍生的底物，类似地开发了 [1+4]/[3+2] 环化序列以产生稠合的环戊二烯 [b] 呋喃结构。
• Asymmetric assembly of 2-oxindole and α-angelica lactone units to construct vicinal quaternary chiral centers
  作者：Xin Huang、Jin Peng、Lin Dong、Ying-Chun Chen

  DOI：10.1039/c2cc17777c

  日期：——

  The first organocatalytic asymmetric assembly of Morita–Baylis–Hillman carbonates of isatins and α-angelica lactone has been studied, affording multifunctional products containing two valuable pharmacophores and vicinal quaternary chiral centers in high stereoselectivity (up to 92% ee, dr >95 : 5).

  我们首次研究了莫里塔-贝利斯-希尔曼碳酸异辛酯和δ-当归内酯的有机催化不对称组装，以高立体选择性（ee高达92%，dr >95â:â5）获得了含有两种有价值药性和副季手性中心的多功能产品。
• Asymmetric α-Regioselective [3 + 2] Annulation of Morita–Baylis–Hillman Carbonates: Construction of Three Contiguous Stereocenters with Vicinal Quaternary Carbon Centers
  作者：Xiaochen Tian、Yongxing Zhang、Hao Dong、Weiwu Ren、Yang Wang

  DOI：10.1021/acs.joc.2c00582

  日期：2022.8.5

  spirocyclic oxindole derivatives containing three contiguous stereogenic centers and vicinal all-carbon quaternary chiral centers. This reaction exhibits a broad substrate scope and excellent functional group tolerance. Excellent yields with high diastereo- and enantioselectivities were obtained in this efficient organocatalytic reaction.

  MBH碳酸酯与4-芳甲基异恶唑-5-酮的不对称α-区域选择性环化得到了含有三个连续立体中心和邻位全碳四元手性中心的螺环羟吲哚衍生物。该反应表现出广泛的底物范围和优异的官能团耐受性。在这种高效的有机催化反应中，获得了具有高非对映选择性和对映选择性的优异产率。