methyl 2-(3-bromo-2-oxoindolin-3-yl)acetate | 104519-70-2

• 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-bromo-2-oxoindolin-3-yl)acetate
• CAS: 104519-70-2
• 化学式: C₁₁H₁₀BrNO₃
• 分子量: 284.109
• InChiKey: LVBDYMCCDGINFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  55.4
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 2-(3-bromo-2-oxoindolin-3-yl)acetate 在 ammonium cerium (IV) nitrate 、 nickel(II) tetrafluoroborate hexahydrate 、 C₄₂H₆₆N₄O₈ 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 24.92h， 生成 methyl R-2-(3-amino-2-oxoindol-3-yl)acetate
  参考文献：
  名称：

  Enantioselective Synthesis of 3‐Substituted 3‐Amino‐2‐oxindoles by Amination with Anilines

  摘要：

  AbstractA chiral N,N′‐dioxide‐nickel(II) complex‐catalyzed asymmetric amination of 3‐bromo‐3‐substituted oxindoles with anilines has been developed. A series of alkyl or aryl 3‐amino‐indolinones with quaternary stereocenters were obtained in high yields with excellent ee values in one step (up to 99 % yield, up to 96 % ee). The method provided a ready route to optically active intermediates of 3‐amino‐2‐oxindole‐based bioactive compounds. Moreover, a possible transition‐state model is proposed so as to elucidate the origin of the chirality based on the X‐ray crystal structure of the catalyst and the adduct.

  DOI：

  10.1002/chem.202100829
• 作为产物：
  描述：

  2-(2-氧代-1,3-二氢吲哚-3-基)乙酸甲酯 在 N-溴代丁二酰亚胺(NBS) 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 methyl 2-(3-bromo-2-oxoindolin-3-yl)acetate
  参考文献：
  名称：

  Enantioselective Synthesis of 3‐Substituted 3‐Amino‐2‐oxindoles by Amination with Anilines

  摘要：

  AbstractA chiral N,N′‐dioxide‐nickel(II) complex‐catalyzed asymmetric amination of 3‐bromo‐3‐substituted oxindoles with anilines has been developed. A series of alkyl or aryl 3‐amino‐indolinones with quaternary stereocenters were obtained in high yields with excellent ee values in one step (up to 99 % yield, up to 96 % ee). The method provided a ready route to optically active intermediates of 3‐amino‐2‐oxindole‐based bioactive compounds. Moreover, a possible transition‐state model is proposed so as to elucidate the origin of the chirality based on the X‐ray crystal structure of the catalyst and the adduct.

  DOI：

  10.1002/chem.202100829

文献信息

• Enantioselective [4 + 2] Cycloaddition/Cyclization Cascade Reaction and Total Synthesis of <i>cis</i>-Bis(cyclotryptamine) Alkaloids
  作者：Jian Xu、Runze Li、Nian Xu、Xiaohua Liu、Fei Wang、Xiaoming Feng

  DOI：10.1021/acs.orglett.1c00260

  日期：2021.3.5

  The asymmetric catalytic synthesis of 3-cyclotryptamine substituted oxindoles through formal [4 + 2] cycloaddition/cyclization cascade is described. A wide range of cyclotryptamine derivatives were obtained in enantioenriched form under mild reaction conditions and were found to have potential anticancer activity. The strategy enables ready assembly of cyclotryptamine subunits at the C3a–C3a′ positions

  描述了通过正式的[4 + 2]环加成/环化级联反应3-环色胺取代的羟吲哚的不对称催化合成。在温和的反应条件下，以对映体富集的形式获得了广泛的环色胺衍生物，发现它们具有潜在的抗癌活性。该策略使C 3a – C 3a'位置的环色胺亚基易于组装，并具有两个四级立体异构中心，具有顺式选择性，从而可以合成光学活性的顺式双（六氢吡咯并吲哚）和环色胺生物碱家族的其他化合物。
• Construction of the N1–C3 Linkage Stereogenic Centers by Catalytic Asymmetric Amination Reaction of 3-Bromooxindoles with Indolines
  作者：Hailong Zhang、Hong Kang、Liang Hong、Weiping Dong、Guolin Li、Xin Zheng、Rui Wang

  DOI：10.1021/ol5007423

  日期：2014.5.2

  The catalytic asymmetric amination reaction of 3-bromooxindoles with indolines for the construction of the N1–C3 linkage stereogenic centers has been realized for the first time. Moreover, the racemic substrates (3-substituted indolines) were also applicable under the same chiral conditions. The newly developed method conveniently led to a formal synthesis of (+)-psychotrimine.

  首次实现了3-溴代吲哚与二氢吲哚的催化不对称胺化反应，用于构建N1-C3键构立体中心。此外，外消旋底物（3-取代的二氢吲哚）也可在相同的手性条件下使用。新开发的方法方便地导致了（+）-精神三胺的正式合成。
• Construction of Vicinal All-Carbon Quaternary Stereocenters Enabled by a Catalytic Asymmetric Dearomatization Reaction of β-Naphthols with 3-Bromooxindoles
  作者：Xihong Liu、Pengxin Wang、Lutao Bai、Dan Li、Linqing Wang、Dongxu Yang、Rui Wang

  DOI：10.1021/acscatal.8b03905

  日期：2018.11.2

  from 3-bromooxindoles was reported. This methodology leads to the efficient construction of a series of enantioenriched 3,3′-disubstituted oxindoles bearing vicinal all-carbon quaternary stereocenters via a dearomatization process of phenols under mild reaction conditions. Additionally, the representative large-scale reactions and related transformations of the dearomatized products reveal the potential

  据报道，有机酚不对称地将芳香族苯酚脱芳香基加成到3-溴代吲哚就地生成的吲哚-2-酮中。该方法学导致在温和的反应条件下，通过苯酚的脱芳香化过程，有效地构建了一系列带有邻位全碳四元立体中心的对映体富集的3,3'-二取代的羟吲哚。另外，脱芳香化产物的代表性大规模反应和相关转化揭示了该方案的潜在合成效用。
• Asymmetric Synthesis of 3-Lactone Substituted 2-Oxindoles with Vicinal Quaternary Carbon Centers via Vinylogous Conjugate Addition
  作者：Zegong Li、Zi Zeng、Qi Tang、Ziwei Zhong、Xiaohua Liu、Xiaoming Feng

  DOI：10.1055/a-2066-2879

  日期：——

  A new method has been developed for constructing vicinal quaternary stereocenters with an oxindole–butanolide hybrid framework through asymmetric vinylogous addition of a siloxyfuran to an indol-2-one in the presence of a readily available N,N′-dioxide–Ni(OTf)2 complex catalyst. Various oxindole–lactones were obtained in up to 98% yield with >19:1 dr and 97% ee under mild reaction conditions. A possible

  开发了一种新方法，通过在容易获得的N , N ' -二氧化物-Ni(OTf)存在下，将甲硅氧呋喃不对称插烯加成到吲哚-2-酮上，从而构建具有羟吲哚-丁内酯杂化骨架的邻位季立体中心2络合物催化剂。在温和的反应条件下，以 >19:1 dr 和 97% ee 获得了高达 98% 的收率和 97% ee 的各种羟吲哚内酯。提出了一种可能的过渡态模型来解释不对称感应的起源。
• Asymmetric catalytic alkylation of vinyl azides with 3-bromo oxindoles: water-assisted chemo- and enantiocontrol
  作者：Ziwei Zhong、Lichao Ning、Yican Lu、Jiuqi Tan、Lili Lin、Xiaoming Feng

  DOI：10.1007/s11426-022-1500-0

  日期：——

  enantioselective alkylation of vinyl azides with 3-bromo-3-substituted oxindoles was achieved through a chiral N,N′-dioxide/Ni(OTf)2-mediated conjugate addition/water addition/elimination tandem process. Water was critical to the chemo- and enantioselectivity. The hydrated Na3PO4 acted as both a base and a reservoir to regulate the amount of water in solution. A wide range of enantioenriched oxindoles having

  通过手性N,N'-二氧化物/Ni(OTf) 2介导的共轭加成/加水/消除串联过程，实现了乙烯基叠氮化物与 3-溴-3-取代羟吲哚的高度化学选择性和对映选择性烷基化。水对化学选择性和对映选择性至关重要。水合 Na 3 PO 4既作为碱基又作为储库来调节溶液中的水量。以良好的产率和良好的 ee 值（51 个实例，高达 90% 的产率，97% ee）获得了具有 α-羰基取代的全碳季立构中心的各种对映体富集的羟吲哚。将产品轻松转化为 (+)-physovenine 和 (+)-desoxyeseroline 的类似物提高了合成价值。包括控制实验、动力学研究和密度泛函理论 (DFT) 计算在内的机理研究支持提出可能的催化循环以及过渡态，以阐明反应过程和手性诱导。