tert-butyl (S)-(5-chloro-3-(nitromethyl)-2-oxoindolin-3-yl)carbamate | 1620006-78-1

• 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 (S)-(5-chloro-3-(nitromethyl)-2-oxoindolin-3-yl)carbamate
• CAS: 1620006-78-1
• 化学式: C₁₄H₁₆ClN₃O₅
• 分子量: 341.751
• InChiKey: ILMHEMXJESMLSR-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  110.57
• 氢给体数：
  2.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  5-氯靛红 在 copper(II) tetrafluroborate hexahydrate 、 (S,S)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) 、 二异丙胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 15.0h， 生成 tert-butyl (S)-(5-chloro-3-(nitromethyl)-2-oxoindolin-3-yl)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。
• Organocatalytic enantioselective aza-Henry reaction of ketimines derived from isatins: access to optically active 3-amino-2-oxindoles
  作者：Akshay Kumar、Jasneet Kaur、Swapandeep Singh Chimni、Amanpreet Kaur Jassal

  DOI：10.1039/c4ra00902a

  日期：——

  An organocatalytic asymmetric aza-Henry reaction of ketimines derived from isatins with nitroalkanes has been achieved using Cinchona alkaloid organocatalysts. This method works efficiently with several ketimines to produce a good (up to 82%) yield of the corresponding 3-substituted 3-amino-2-oxindoles with a good (up to 89%) enantiomeric excess.

  使用金鸡纳生物碱有机催化剂已经实现了衍生自靛红的酮亚胺与硝基烷烃的有机催化不对称氮杂-亨利反应。该方法与几种酮亚胺一起有效地起作用，以良好的对映体过量（高达89％）产生相应的3-取代的3-氨基-2-氧吲哚的良好的产率（高达82％）。
• 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.