1-benzyl-3-hydroxy-5-methyl-3-phenylindolin-2-one

• 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-benzyl-3-hydroxy-5-methyl-3-phenylindolin-2-one
• 英文别名: 1-Benzyl-3-hydroxy-5-methyl-3-phenylindol-2-one；1-benzyl-3-hydroxy-5-methyl-3-phenylindol-2-one
• 化学式: C₂₂H₁₉NO₂
• 分子量: 329.398
• InChiKey: QXLVHGAXBAKQEW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-benzyl-3-hydroxy-5-methyl-3-phenylindolin-2-one 在 叠氮基三甲基硅烷 、 三氟乙酸 作用下， 以95 %的产率得到1-benzyl-6-methyl-3-phenylquinoxalin-2(1H)-one
  参考文献：
  名称：

  Expanding the Potential of 3‐Hydroxyindolinones: Synthesis of Quinoxalin‐2(1H)‐ones through Acid‐Promoted Azidation and Ring‐Expansion

  摘要：

  摘要 我们在此报告了一种从 3-羟基吲哚啉-2-酮衍生物合成喹喔啉-2(1H)-酮的方法。该反应是通过一个碳位化合物在 CF3CO2H 介导下发生叠氮反应，然后在酸的诱导下发生 N2 挤压和扩环反应。研究发现，CF3CO2H 和溶剂 1,1,1,3,3,3-六氟-2-丙醇对这一重排反应至关重要。产物中完全保留了 3-hydroxyindolin-2-one 骨架的轴向手性。

  DOI：

  10.1002/adsc.202300685
• 作为产物：
  描述：

  溴甲苯 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 1.25h， 生成 1-benzyl-3-hydroxy-5-methyl-3-phenylindolin-2-one
  参考文献：
  名称：

  AC=O⋅⋅⋅Isothiouronium 相互作用决定了叔杂环醇酰基化动力学拆分中的对映体区别

  摘要：

  实验和计算研究的结合已经确定 C=O⋅⋅⋅isothiouronium 相互作用是在立体叔甲醇中心承载多达三个潜在识别基序的叔杂环醇的动力学分辨率中有效对映体区分的关键。这种区分在异硫脲催化的叔杂环醇的酰基化动力学拆分中得到了利用（38 个例子，s 因子高达 >200）。该反应在低催化剂负载量（通常为 1 mol%）下进行，异丁酸或乙酸酐作为酰化剂在温和条件下进行。

  DOI：

  10.1002/anie.201712456

文献信息

• A C=O⋅⋅⋅Isothiouronium Interaction Dictates Enantiodiscrimination in Acylative Kinetic Resolutions of Tertiary Heterocyclic Alcohols
  作者：Mark D. Greenhalgh、Samuel M. Smith、Daniel M. Walden、James E. Taylor、Zamira Brice、Emily R. T. Robinson、Charlene Fallan、David B. Cordes、Alexandra M. Z. Slawin、H. Camille Richardson、Markas A. Grove、Paul Ha‐Yeon Cheong、Andrew D. Smith

  DOI：10.1002/anie.201712456

  日期：2018.3.12

  C=O⋅⋅⋅isothiouronium interaction as key to efficient enantiodiscrimination in the kinetic resolution of tertiary heterocyclic alcohols bearing up to three potential recognition motifs at the stereogenic tertiary carbinol center. This discrimination was exploited in the isothiourea‐catalyzed acylative kinetic resolution of tertiary heterocyclic alcohols (38 examples, s factors up to >200). The reaction proceeds at low

  实验和计算研究的结合已经确定 C=O⋅⋅⋅isothiouronium 相互作用是在立体叔甲醇中心承载多达三个潜在识别基序的叔杂环醇的动力学分辨率中有效对映体区分的关键。这种区分在异硫脲催化的叔杂环醇的酰基化动力学拆分中得到了利用（38 个例子，s 因子高达 >200）。该反应在低催化剂负载量（通常为 1 mol%）下进行，异丁酸或乙酸酐作为酰化剂在温和条件下进行。
• Nickel(II)-catalyzed addition reaction of arylboronic acids to isatins
  作者：Yu-Yang Zhang、Huixuan Chen、Xiaoding Jiang、Hao Liang、Xuefeng He、Yaqi Zhang、Xiangmeng Chen、Wenhuan He、Yongsu Li、Liqin Qiu

  DOI：10.1016/j.tet.2018.03.039

  日期：2018.5

  A Ni-catalyzed addition of arylboronic acids to isatins was first developed. The reaction, driven by Ni(acac)2 and dppp as the phosphine ligand, gave 3-aryl-3-hydroxy-2-oxindoles in up to 97% yield. Scopes of benzyl-protected isatins and arylboronic acids were examined. Substituted phenylboronic acids along with fused-ring and heterocyclic boronic acids reacted with isatins smoothly. Preliminary asymmetric

  首先开发了Ni催化的芳基硼酸到靛红的加成反应。在Ni（acac）2和dppp作为膦配体的驱动下，该反应以高达97％的收率得到3-芳基-3-羟基-2-氧吲哚。检查了苄基保护的靛红和芳基硼酸的范围。取代的苯基硼酸与稠环和杂环硼酸一起与靛红平稳地反应。还初步研究了不对称催化，显示出中等的对映选择性。还描述了该机制。
• Evaluating polymer-supported isothiourea catalysis in industrially-preferable solvents for the acylative kinetic resolution of secondary and tertiary heterocyclic alcohols in batch and flow
  作者：Nitul Ranjan Guha、Rifahath M. Neyyappadath、Mark D. Greenhalgh、Ross Chisholm、Samuel M. Smith、Megan L. McEvoy、Claire M. Young、Carles Rodríguez-Escrich、Miquel A. Pericàs、Georg Hähner、Andrew D. Smith

  DOI：10.1039/c8gc02020e

  日期：——

  acylative kinetic resolution of secondary and tertiary heterocyclic alcohols. In batch, the use of industrially-preferable solvents was investigated, with dimethyl carbonate proving to be most generally-applicable. Significantly, the HyperBTM-derived immobilised catalysts were readily recycled, with no loss in either activity or selectivity. In addition to the kinetic resolution of secondary benzylic, propargylic

  已经合成了基于均相异硫脲HyperBTM和BTM的聚合物负载的路易斯碱催化剂，并将其用于仲和叔杂环醇的酰基动力学拆分。分批地，研究了工业上优选的溶剂的使用，其中碳酸二甲酯被证明是最普遍适用的。重要的是，HyperBTM衍生的固定化催化剂易于回收利用，而活性或选择性均没有损失。除了动力学拆分二级苄基，炔丙基，烯丙基和环烷醇衍生物外，还基于优选的3-羟基羟吲哚和3-羟基吡咯烷酮亚结构对22种叔杂环醇进行了分离，分离度高达出色的（s= 7–190）。最后，将固定化的异硫脲催化剂应用于填充床反应器中，以证明连续流动过程中叔杂环醇动力学拆分的第一个实例。3-hydroxyoxindole衍生物在乙酸乙酯（分辨率获得高选择性š高达70）; 和3- hydroxypyrrolidinones衍生物在甲苯（š高达42）。
• Axial Tri-<i>tert</i>-butylphosphane Coordination to Rh₂(OAc)₄: Synthesis, Structure, and Catalytic Studies
  作者：Jiantao Tan、Yi Kuang、Yi Wang、Qingfei Huang、Jin Zhu、Yuanhua Wang

  DOI：10.1021/acs.organomet.6b00477

  日期：2016.9.26

  The introduction of strong sigma-donor axial ligands to the Rh-Rh metal bond has been utilized as an effective way to provide new chemical reactivities to bimetallic dirhodium(II) complexes. In this report, Rh-2(OAc)(4) complexes with axial bulky alkylphosphane ligands (PR3), in particular P(t- Bu)(3), were prepared and characterized. The net sigma-donation from the PR3 to the Rh-Rh bond is the result of the competition between the electron-donating ability of the R group and the steric profile of the PR3 at the Rh-2 core. Analysis of the crystal structure data showed that the strong sigma-donor P(t-Bu)(3) coordinates to the rhodium with an amount of sigma-donation to the rhodium similar to that of the aryl phosphane ligand PPh3, but has an unusually long Rh-P bond distance (2.663 angstrom). During catalytic trials to synthesize 3-aryl-3-hydroxy-2-oxindole by the addition of arylboronic acids to isatin derivatives, this longer Rh-P bond distance in Rh-2(OAc)(4)(P(t-Bu)(3))(2) (Cat-1) facilitates substitution of one of the axial phosphane ligands by the arylboronic acid. This sigma-donating effect greatly accelerated the arylation reaction in comparison to alternative catalysts. Additionally, Rh-2(OAc)(4) was easily recovered after completion of the reaction.
• Arylboronic Acid-Catalyzed Racemization of Secondary and Tertiary Alcohols
  作者：Gregory R. Boyce、Stefania F. Musolino、Jianing Yang、Andrew D. Smith、James E. Taylor

  DOI：10.1021/acs.joc.2c01602

  日期：2022.10.7

  The use of 2-carboxyphenylboronic acid (5 mol %) and oxalic acid (10 mol %) with 2-butanone as a solvent for the racemization of a range of enantiomerically pure secondary and tertiary alcohols is demonstrated. The process is postulated to proceed via reversible Brønsted acid-catalyzed C–O bond cleavage through an achiral carbocation intermediate.

  演示了使用 2-羧基苯基硼酸 (5 mol%) 和草酸 (10 mol%) 与 2-丁酮作为溶剂对一系列对映体纯的仲醇和叔醇进行消旋化。假设该过程通过非手性碳阳离子中间体通过可逆的布朗斯台德酸催化的 C-O 键裂解进行。