3-(4-bromophenyl)-3-hydroxy-4-(N,N-dimethylaminocarbonyl)indolin-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: 3-(4-bromophenyl)-3-hydroxy-4-(N,N-dimethylaminocarbonyl)indolin-2-one
• 英文别名: (3S)-3-(4-bromophenyl)-3-hydroxy-N,N-dimethyl-2-oxo-1H-indole-4-carboxamide
• 化学式: C₁₇H₁₅BrN₂O₃
• 分子量: 375.222
• InChiKey: ZPRQJTLOQCIQAI-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  69.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(4-溴苯基)-2-氧代乙酸 在 吡啶 、 草酰氯 、 [Ir(cod)2]BARF 、 C₅₀H₄₂N₂OP₂ 、 N,N-二甲基甲酰胺 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 3-(4-bromophenyl)-3-hydroxy-4-(N,N-dimethylaminocarbonyl)indolin-2-one
  参考文献：
  名称：

  阳离子Ir / Me-BIPAM催化的α-酮酰胺的不对称分子内直接氢芳基化反应

  摘要：

  α-酮酰胺的不对称分子内直接氢芳基化反应可高产率获得各种类型的旋光3-取代3-羟基2-羟吲哚，具有完全的区域选择性和高对映选择性（84–98％ee）。这是通过使用阳离子铱络合物[Ir（cod）2 ]（BAr F 4）和手性O联双齿亚磷酰胺（R，R）-Me-BIPAM来实现的。

  DOI：

  10.1002/anie.201400147

文献信息

• Scope and Mechanistic Studies of the Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation Reaction
  作者：Tomohiko Shirai、Yasunori Yamamoto

  DOI：10.1021/om501260w

  日期：2015.7.27

  Results of mechanistic studies on asymmetric hydroarylation of alpha-keto amides Via direct C-H bond addition to a carbonyl group catalyzed by a cationic Ir/Me-BIPAM complex are presented in this paper. A catalytic cycle involving C-H bond cleavage to give an Ar-[Ir](+) intermediate, insertion of a carbonyl group into the aryl-iridium bond, giving iridium alkoxide, and finally reductive elimination to reproduce active [Ir](+) species is proposed. The mechanistic insight for the iridium hydride species indicated that the C-H bond cleavage is caused in a reversible manner. Furthermore, the kinetic isotope effect was measured by product analysis of the reaction to compare HID, and it was determined that k(H)/k(D) was 1.85. These experimental results suggest that the C-H bond cleavage step is not included hi the turnover-limiting step. In addition, Hammett studies of substrates (rho = -0.99) demonstrated that electron-donating groups at the para position to the reactive C-H bond accelerate the reaction rate. This linear relationship obtained in the Hammett plot indicates that the nucleophilicity of the aryl-iridium intermediate is an important factor in this reaction. All of the data indicate that carbonyl insertion into aryl-iridium is included in the turnover-limiting step of the catalytic cycle.
• Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of α-Ketoamides
  作者：Tomohiko Shirai、Hajime Ito、Yasunori Yamamoto

  DOI：10.1002/anie.201400147

  日期：2014.3.3

  Asymmetric intramolecular direct hydroarylation of α‐ketoamides gives various types of optically active 3‐substituted 3‐hydroxy‐2‐oxindoles in high yields with complete regioselectivity and high enantioselectivities (84–98 % ee). This is realized by the use of the cationic iridium complex [Ir(cod)2](BArF4) and the chiral O‐linked bidentate phosphoramidite (R,R)‐Me‐BIPAM.

  α-酮酰胺的不对称分子内直接氢芳基化反应可高产率获得各种类型的旋光3-取代3-羟基2-羟吲哚，具有完全的区域选择性和高对映选择性（84–98％ee）。这是通过使用阳离子铱络合物[Ir（cod）2 ]（BAr F 4）和手性O联双齿亚磷酰胺（R，R）-Me-BIPAM来实现的。