tert-butyl (6-chloro-2-oxoindolin-3-ylidene)carbamate | 1620006-68-9

• 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: tert-butyl (6-chloro-2-oxoindolin-3-ylidene)carbamate
• CAS: 1620006-68-9
• 化学式: C₁₃H₁₃ClN₂O₃
• 分子量: 280.711
• InChiKey: WCNZVDNELCGHQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  67.76
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (6-chloro-2-oxoindolin-3-ylidene)carbamate 在 tin(II) chloride dihdyrate 、 (S,S)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) 、 苯硫酚 、 三乙胺 、 copper(ll) bromide 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 22.33h， 生成 methyl (S,E)-4-(3-((tert-butoxycarbonyl)amino)-6-chloro-2-oxoindolin-3-yl)-4-(hydroxyimino)butanoate
  参考文献：
  名称：

  靛蓝酮亚胺与4-硝基丁酸甲酯的Aza-Henry反应生成螺[哌啶-3,3'-羟吲哚]。

  摘要：

  描述了从靛蓝酮亚胺向螺[哌啶-3,3'-羟吲哚]的新对映选择性途径。在Ph 2 BOX-CuBr 2配合物的存在下，N -Boc-isatin酮亚胺与4-硝基丁酸甲酯的aza-Henry反应提供了具有良好的非对映选择性和出色的对映选择性（最高> 99％ee）的相应硝基氨基酯。在将硝基还原为肟，裂解N- Boc基团和内酰胺化之后，将氮杂-亨利加合物转化为螺[哌啶-3,3'-羟吲哚] 。

  DOI：

  10.1002/adsc.201500716
• 作为产物：
  描述：

  6-氯靛红 、 N-BOC-脒三苯基膦 以 1,4-二氧六环 为溶剂， 以63%的产率得到tert-butyl (6-chloro-2-oxoindolin-3-ylidene)carbamate
  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。
• 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。
• Remote C6-Enantioselective C–H Functionalization of 2,3-Disubstituted Indoles through the Dual H-Bonds and π–π Interaction Strategy Enabled by CPAs
  作者：Jia Zhou、Guo-Dong Zhu、Le Wang、Fu-Xin Tan、Wei Jiang、Zhi-Gang Ma、Jun-Chen Kang、Si-Hua Hou、Shu-Yu Zhang

  DOI：10.1021/acs.orglett.9b03276

  日期：2019.11.1

  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.
• 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.