(S)-ethyl 2-(2-iodobenzyl)indoline-2-carboxylate | 1394351-04-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-ethyl 2-(2-iodobenzyl)indoline-2-carboxylate
• CAS: 1394351-04-2
• 化学式: C₁₈H₁₈INO₂
• 分子量: 407.251
• InChiKey: PNTZGZCMVCIMKH-GOSISDBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  38.33
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-ethyl 2-(2-iodobenzyl)indoline-2-carboxylate 在 palladium on activated charcoal 、 氢气 作用下， 以 甲醇 为溶剂， 生成 (R)-ethyl 2-benzylindoline-2-carboxylate
  参考文献：
  名称：

  Copper-Catalyzed Enantioselective Intramolecular N-Arylation, an Efficient Method for Kinetic Resolutions

  摘要：

  For the first time, copper-catalyzed intramolecular N-arylation was successfully applied to the kinetic resolution strategy. Under the catalysis of Cul-BINOL derived ligands, the kinetic resolution of rac-2-amino-3-(2-iodoaryl)propionates and rac-2-amino-4-(2-iodoaryl)butanoates afforded chiral intramolecular coupling products and recovered the starting materials in high enantioselectivity (s factors up to 245).

  DOI：

  10.1021/ol401449b
• 作为产物：
  描述：

  在 盐酸 、 copper(l) iodide 、 水 、 caesium carbonate 、 (S)-(-)-3-3′-双(3,5-双(三氟甲基)苯基)-1,1′-二-2-萘酚 作用下， 以 1,4-二氧六环 、 乙醇 为溶剂， 反应 10.0h， 生成 (S)-ethyl 2-(2-iodobenzyl)indoline-2-carboxylate
  参考文献：
  名称：

  Copper-Catalyzed Desymmetric Intramolecular Ullmann C–N Coupling: An Enantioselective Preparation of Indolines

  摘要：

  The first highly enantioselective copper-catalyzed intramolecular Ullmann C-N coupling reaction has been developed. The asymmetric desymmetrization of 1,3-bis(2-iodoaryl)propan-2-amines catalyzed by CuI/(R)-BINOL-derived ligands led to the enantioselective formation of indolines in high yields and excellent enantiomeric excesses. This method was also applied to the formation of 1,2,3,4-tetrahydroquinolines in high yields and excellent enantioselectivity.

  DOI：

  10.1021/ja306631z

文献信息

• -Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
  作者：Zhiqiang Ding、Nan Nie、Tian Chen、Lingxin Meng、Gongshu Wang、Zhangpei Chen、Jianshe Hu

  DOI：10.1016/j.tet.2020.131826

  日期：2021.1

  developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an l-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized

  开发了一种基于1-脯氨酸N-氧化物/ CuI的新型催化系统，并将其应用于各种N-和O-亲核试剂与芳基碘化物和溴化物的交叉偶联反应。该策略的特征在于使用1-脯氨酸衍生的二酰肼N-氧化物作为优良的支持配体。通过使用该协议，可以以高达99％的产率合成包括N-芳基咪唑，N-芳基吡唑，N-芳基吡咯，N-芳基胺和芳基醚在内的多种产品。
• 螺双二氢苯并噻咯二酚类化合物、合成方法及 其应用
  申请人：中国科学院上海有机化学研究所

  公开号：CN111217848B

  公开（公告）日：2021-11-02

  本发明公开了一种如式I所示的螺双二氢苯并噻咯二酚类化合物、合成方法及其应用。本发明提供了一种高效地通过使用廉价易得的初始原料构建如式I所示的螺双二氢苯并噻咯二酚类化合物的方法，该方法具有操作简便、原料易得，反应条件温和、高收率、方便提纯等特点。本发明提供的如式I所示的螺双二氢苯并噻咯二酚类化合物可以直接作为有机催化剂，或者与第三到第十三族金属盐生成金属配合物或者原位混合使用，用于催化不对称有机合成反应；能在温和的条件下，高效的实现优秀的产率、立体专一性转化，具有良好的底物普适性，极大程度上拓展了不对称催化的研究进程。
• Development and Challenges in Copper-Catalyzed Asymmetric Ullmann-Type Coupling Reactions
  作者：Qian Cai、Fengtao Zhou

  DOI：10.1055/s-0032-1317866

  日期：——

  Ullmann-type coupling is one of the most powerful methods for the formation of aryl C–C, C–N, and C–O bonds. Yet asymmetric Ullmann coupling has received little attention because of the great challenges in both ligand and reaction designs. The success of the first catalytic enantioselective intramolecular Ullmann C–N coupling reaction through an asymmetric desymmetrization strategy offers a new way

  Ullmann 型偶联是形成芳基 C-C、C-N 和 C-O 键的最有效方法之一。然而，由于配体和反应设计中的巨大挑战，不对称 Ullmann 偶联很少受到关注。通过不对称去对称化策略的第一个催化对映选择性分子内 Ullmann C-N 偶联反应的成功为开发此类反应的对映选择性变体提供了一种新方法。本文阐述了去对称化策略在 Ullmann 型耦合中的重要性，并概述了该领域的一些未来方向。
• An Unexpected Inversion of Enantioselectivity in a Copper-Catalyzed Intramolecular­ Desymmetric Aryl C–N Coupling Reaction
  作者：Jiangguang Liu、Jiajie Yan、Dongguang Qin、Qian Cai

  DOI：10.1055/s-0033-1338638

  日期：——

  Enantioselective formation of indolines was achieved through desymmetrization of alpha,alpha-bis(2-iodobenzyl)glycines under the catalysis of copper(I) iodide and (2S, 3aS, 7aS)-octahydro-1H-indole-2-carboxylic acid. An unexpected inversion of enantioselectivity was observed when achiral additives such as 4-(N,N-dimethylamino)pyridine were added which work together with the ligand. The configuration-reversed products were obtained in moderate yields as well as moderate ee values.