| 1467758-65-1

• 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
• CAS: 1467758-65-1
• 化学式: C₁₃H₁₃N₃O₅
• 分子量: 291.263
• InChiKey: OJXSLSWXBBMMCU-UHFFFAOYSA-N

物化性质

• 密度：
  1.43±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  110.9
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2,3-二甲基吲哚 、 在 (11aS)-3,7-di-9-anthracenyl-10,11,12,13-tetrahydro-5-hydroxy-5-oxide diindeno[7,1de:10,70-fg][1,3,2] dioxaphosphocin 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以73%的产率得到tert-butyl (S)-(3-(2,3-dimethyl-1H-indol-6-yl)-5-nitro-2-oxoindolin-3-yl)carbamate
  参考文献：
  名称：

  Remote C6-Enantioselective C–H Functionalization of 2,3-Disubstituted Indoles through the Dual H-Bonds and π–π Interaction Strategy Enabled by CPAs

  摘要：

  A versatile dual H-bonds and π-π interaction strategy that enables enantioselective remote C6-selective C-H functionalization of 2,3-disubstituted indoles was first reported. The N-H bond of indole was pivotal to achieve the C6 functionalization with excellent yield and enantioselectivity. Furthermore, this methodology leads to the efficient construction of numerous enantioenriched C6-functionalized indole products under mild reaction conditions employing different electrophiles. Preliminary cell proliferation investigations revealed that the synthesized chiral C6-substituted indole derivatives had potential anticancer activities.

  DOI：

  10.1021/acs.orglett.9b03276
• 作为产物：
  描述：

  5-硝基靛红 、 N-BOC-脒三苯基膦 以 1,4-二氧六环 为溶剂， 生成
  参考文献：
  名称：

  与Isatin N-Boc酮亚胺的高度对映选择性aza-Henry反应。

  摘要：

  描述了使用Cu（II）-BOX配合物作为催化剂与靛红N-Boc酮亚胺的高度对映选择性氮杂-亨利反应。该反应不需要保护N 1原子，从而提供了带有季立体中心的相应硝胺，具有高收率和对映体过量（高达99.9％）。

  DOI：

  10.1039/c4cc04051a

文献信息

• Recyclable chiral Cu(II) macrocyclic salen complex catalyzed enantioselective aza-Henry reaction of isatin derived N-Boc ketimines and its application for the synthesis of β-diamine
  作者：Tusharkumar Menapara、Manoj K. Choudhary、Rajkumar Tak、Rukhsana I. Kureshy、Noor-ul H. Khan、Sayed H.R. Abdi

  DOI：10.1016/j.molcata.2016.05.021

  日期：2016.9

  Abstract Recyclable chiral Cu(II) macrocyclic salen complex Cu(II)-7 generated in situ efficiently catalyzed asymmetric aza-Henry reaction of various isatin derived N-Boc ketimines with nitromethane as nucleophile at RT to give a high yield (88%) of β-nitro amines with excellent chiral induction (ee, up to 99%) with the added advantage of six times catalyst recyclability. This catalytic system also

  摘要 原位生成的可回收手性 Cu(II) 大环Salen 配合物 Cu(II)-7 在室温下高效催化各种靛红衍生的 N-Boc 酮亚胺与硝基甲烷作为亲核试剂的不对称氮杂亨利反应，得到高产率 (88%) β-硝基胺具有出色的手性诱导（ee，高达 99%），并具有六倍催化剂可回收性的额外优势。该催化体系还可以与硝基乙烷和硝基戊烷很好地协同工作，以中等收率提供相应的产物，并对主要非对映异构体具有高对映选择性。该协议还用于通过 N-Boc 酮亚胺 (1b) 的不对称氮杂-亨利反应合成对映体纯 (S)-β-二胺，该反应分为两步，产率高，对映选择性高。
• Highly Chemo-, Site-, and Enantioseletive <i>para</i> C–H Aminoalkylation of <i>N</i>-Monosubstituted Aniline Derivatives Affording 3-Amino-2-oxindoles
  作者：Chang Liu、Fu-Xin Tan、Jia Zhou、He-Yuan Bai、Tong-Mei Ding、Guo-Dong Zhu、Shu-Yu Zhang

  DOI：10.1021/acs.orglett.0c00262

  日期：2020.3.20

  In general, enantioselective C–H functionalization of N-monosubstituted anilines is a highly challenging task owing to the competitive chemoselective N–H bond insertion reactions. In this paper, we reported a direct highly chemo-, site-, and enantioselective para C–H aminoalkylation of N-monosubstituted aniline derivatives with isatin-derived ketimines in the presence of chiral phosphoric acids (CPAs)

  通常，由于竞争性的化学选择性NH键插入反应，N-单取代苯胺的对映选择性CH官能团是一项极富挑战性的任务。在本文中，我们报道了在手性磷酸（CPA）存在下，N-单取代的苯胺衍生物与Isatin衍生的酮亚胺的直接高度化学，位点和对映选择性对C–H氨基烷基化，并提供了对位磷酸的实用策略含NH键的苯胺的不对称CH功能化。
• 一种手性/消旋6-取代吲哚类化合物的制备方法
  申请人：上海交通大学

  公开号：CN112430206B

  公开（公告）日：2022-03-18

  本发明涉及一种手性/消旋6‑取代吲哚类化合物的制备方法，将靛红亚胺与吲哚化合物溶于溶剂中，在手性/消旋磷酸催化剂的作用下发生Friedel‑Crafts反应，制备得到手性/消旋6‑取代吲哚衍生物。与现有技术相比，本发明无需金属参与，不使用导向基团、产率高、对映选择性可控，为6位取代的吲哚类化合物的合成提供了新的途径，制得的化合物对几种人类癌细胞的增殖有抑制作用，可能为肿瘤治疗提供一种潜在的策略，具有很好的应用前景。
• Gold‐Catalyzed Formal [4+2] Cycloaddition as Access to Antitumor‐Active Spirocyclic Oxindoles from Alkynes and Isatin‐Derived Ketimines
  作者：Yaowen Liu、Martin C. Dietl、Robin Heckershoff、Chunyu Han、Hongwei Shi、Matthias Rudolph、Frank Rominger、Isabella Caligiuri、Kanwal Asif、Muhammad Adeel、Thomas Scattolin、A. Stephen K. Hashmi

  DOI：10.1002/anie.202304672

  日期：2023.8.21

  for the synthesis of spirooxindoles that possess excellent antiproliferative activity on human tumor cell lines was achieved through a gold-catalyzed cycloaddition reaction of alkynes with isatin-derived ketimines. Various functionalized and readily available alkynes reacted under mild reaction conditions.

  通过金催化的炔烃与靛红衍生的酮亚胺的环加成反应，实现了一种新的合成螺环吲哚的方案，该螺环吲哚对人肿瘤细胞系具有优异的抗增殖活性。各种官能化且易于获得的炔烃在温和的反应条件下发生反应。
• Isatin N-protected ketimines with nitromethane catalyzed by chiral binol linked monomeric macrocyclic Cu(II)–salen complex
  作者：Tusharkumar Menapara、Raj kumar Tak、S. Saravanan、Rukhsana I. Kureshy、Noor-ul H. Khan、B. Ganguly、Mrinal Kanti Si

  DOI：10.1016/j.tet.2018.10.001

  日期：2018.12

  Chiral Cu-1B generated in situ was used as an efficient catalyst for the synthesis of beta-nitroamines in high yield (88%) with excellent enantioselectivity (ee up to 99%) at RT in absence of co-catalyst via asymmetric aza-Henry reaction of various isatin derived N-Boc ketimines with nitromethane. This catalytic system did not work well with other nitroalkanes under the above optimized reaction conditions. To examine this catalytic behaviour, quantum chemical DFT calculations were performed with the nucleophiles (CH2NO2- and CH3CHNO2-) for the conversion of la to 2a using macrocyclic Cu-1B complex. The DFT calculated results have shown that the reaction with CH2NO2- is more favourable than the corresponding CH3CHNOy. The calculated activation barriers suggest that the reaction with CH2NO2- is -8.0 kcal/mol energetically favoured than CH3CHNO2-. This catalytic protocol was further used to obtain chiral beta-diamines (a building block for pharmaceuticals) at gram scale. In order to elucidate the reaction mechanism of asymmetric aza Henry reaction kinetic experiments were performed with different concentrations of the catalyst Cu-1B, nitromethane and 1g as the representative substrate. The reaction of isatin N-Boc ketimine was first order with respect to the concentration of the catalyst and the nitromethane but did not depend on the initial concentration of the substrate. A possible mechanism for the aza Henry reaction was proposed. (C) 2018 Elsevier Ltd. All rights reserved.