tert-butyl (7-chloro-2-oxoindolin-3-ylidene)carbamate | 1620006-69-0

• 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: tert-butyl (7-chloro-2-oxoindolin-3-ylidene)carbamate
• CAS: 1620006-69-0
• 化学式: C₁₃H₁₃ClN₂O₃
• 分子量: 280.711
• InChiKey: DOGSKCPUNIGFEK-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 (7-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 17.33h， 生成 methyl (S,E)-4-(3-((tert-butoxycarbonyl)amino)-7-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：

  7-氯靛红 、 N-BOC-脒三苯基膦 以 1,4-二氧六环 为溶剂， 以96%的产率得到tert-butyl (7-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

• 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.