2-(1-benzyl-3-hydroxy-2-oxoindolin-3-yl)acetonitrile

• 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: 2-(1-benzyl-3-hydroxy-2-oxoindolin-3-yl)acetonitrile
• 英文别名: 1-benzyl-3-cyanomethyl-3-hydroxy-oxindole；2-(1-Benzyl-3-hydroxy-2-oxoindol-3-yl)acetonitrile
• 化学式: C₁₇H₁₄N₂O₂
• 分子量: 278.31
• InChiKey: FIMMPLGPIYTIHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  64.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(1-benzyl-3-hydroxy-2-oxoindolin-3-yl)acetonitrile 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 以81%的产率得到(+/-)-8-benzyl-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indol-3a-ol
  参考文献：
  名称：

  A [3 + 2] Dipolar Cycloaddition Route to 3-Hydroxy-3-alkyl Oxindoles: An Approach to Pyrrolidinoindoline Alkaloids

  摘要：

  A [3 + 2] cycloaddition approach to the 3-hydroxy-3-alkyl oxindole scaffold is described. Isoxazolines obtained by cycloaddition of nitrile oxide 3 with 3-methylene oxindoles were elaborated to 3-hydroxy-3-cyanomethyl oxindoles employing a one-pot protocol en route to the pyrrolidinoindoline moiety which is found in many natural products. The total syntheses of alkaloids (+/-)-alline and (+/-)-CPC-1 were achieved using this methodology.

  DOI：

  10.1021/ol200547m
• 作为产物：
  描述：

  3-亚甲基氧化吲哚 在 potassium acetate 、 caesium carbonate 作用下， 以 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 17.0h， 生成 2-(1-benzyl-3-hydroxy-2-oxoindolin-3-yl)acetonitrile
  参考文献：
  名称：

  A [3 + 2] Dipolar Cycloaddition Route to 3-Hydroxy-3-alkyl Oxindoles: An Approach to Pyrrolidinoindoline Alkaloids

  摘要：

  A [3 + 2] cycloaddition approach to the 3-hydroxy-3-alkyl oxindole scaffold is described. Isoxazolines obtained by cycloaddition of nitrile oxide 3 with 3-methylene oxindoles were elaborated to 3-hydroxy-3-cyanomethyl oxindoles employing a one-pot protocol en route to the pyrrolidinoindoline moiety which is found in many natural products. The total syntheses of alkaloids (+/-)-alline and (+/-)-CPC-1 were achieved using this methodology.

  DOI：

  10.1021/ol200547m

文献信息

• Catalytic nucleophilic activation of acetonitrile via a cooperative catalysis of cationic Ru complex, DBU, and NaPF6
  作者：Naoya Kumagai、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2007.04.051

  日期：2007.8

  mild amine basic conditions is described. A cooperative catalysis of CpRu complex, DBU, and NaPF6 enables chemoselective and catalytic generation of nucleophiles from barely acidic acetonitrile, which is integrated into the addition to aldehydes, imines, and activated ketones. Mechanistic investigations revealed that the three catalyst components work together to achieve high catalytic efficiency.

  描述了在温和的胺碱性条件下直接添加乙腈的有效催化系统的开发。CpRu络合物，DBU和NaPF 6的协同催化能够从勉强酸性的乙腈进行化学选择和催化生成亲核试剂，并将其整合到醛，亚胺和活化的酮中。机理研究表明，三种催化剂组分共同作用以实现高催化效率。
• An efficient route to synthesize isatins by metal-free, iodine-catalyzed sequential C(sp³)–H oxidation and intramolecular C–N bond formation of 2′-aminoacetophenones
  作者：Venkatachalam Rajeshkumar、Selvaraj Chandrasekar、Govindasamy Sekar

  DOI：10.1039/c4ob01564a

  日期：——

  A novel molecular I2-catalyzed synthesis of isatins through C(sp3)–H oxidation and intramolecular C–N bond formation of 2′-aminoacetophenones with excellent yields up to 97% under transition metal, base, additive, peroxide and ligand free conditions is described. The present protocol is suitable for gram scale synthesis of isatins and retained its high yield. Further, the synthetic utility of this

  通过C（sp 3）–H氧化和2'-氨基苯乙酮的分子内C–N键形成的新型分子I 2催化的靛红合成，在不含过渡金属，碱，添加剂，过氧化物和配体的情况下，产率高达97％描述了条件。本协议适用于伊斯汀的克规模合成，并保持其高产率。此外，证明了该反应对生物活性3-羟基-2-氧吲哚和氧吲哚的合成的合成效用。
• An efficient aldol-type direct reaction of isatins with TMSCH₂CN
  作者：V. U. Bhaskara Rao、Krishna Kumar、Ravi P. Singh

  DOI：10.1039/c5ob01560j

  日期：——

  Cesium fluoride catalyzed direct cyanomethylation of various isatins by using trimethylsilyl acetonitrile (TMSAN) as a nucleophile has been developed. The reaction has been explored for a number of isatins, with various substitutions on its aromatic ring. Further, the versatility of the reaction is demonstrated by converting the direct aldol adducts to various corresponding intermediates.

  通过使用三甲基硅乙腈（TMSAN）作为亲核试剂，氟化铯催化的直接氰甲基化反应已被开发用于各种吲哚酮的反应。该反应已经应用于多种带有芳环取代的吲哚酮。此外，通过将直接醛醇加合物转化为各种相应的中间体，证明了该反应的多功能性。
• Nickel‐Catalyzed Cyanoalkylation of Ketone Derivatives
  作者：Anaïs Coffinet、Vincent Levacher、Isabelle Gillaizeau、Jean‐François Brière、Sylvain Oudeyer

  DOI：10.1002/adsc.202201147

  日期：2023.1.24

  Although the metal-based catalyzed cyanomethylation of aldehydes is well-developed, a similar approach to ketones with acetonitrile derivatives remains a challenge. Thanks to Tolman type complexes, NiII-complexes with a pyridine(dicarboxamide) pincer ligand, an alternative metal-catalyzed (1–5 mol% catalyst) cyanomethylation of an array of isatins and activated ketones is reported at room temperature

  尽管基于金属的催化醛类氰甲基化反应已经很成熟，但用乙腈衍生物对酮类进行类似的催化反应仍然是一个挑战。多亏了 Tolman 型配合物，Ni II配合物与吡啶（二甲酰胺）钳形配体，一种替代的金属催化（1-5 mol% 催化剂）在室温下对一系列靛红和活化酮进行氰甲基化。不仅使用弱酸性乙腈，而且使用更具挑战性的取代烷基氰化物亲核试剂，都获得了高分离产率（高达 99%）。原位生成的假定离子对催化剂 [NiCR 2 CN] - Cat +可能受益于阳离子部分（Cs +或n -Bu 4 N + ) 以促进它们的形成和催化活性。