1-cyclohexylcarbonyl-1,2-hydrazinedicarboxylic acid 1,2-diisopropyl ester

• 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: 1-cyclohexylcarbonyl-1,2-hydrazinedicarboxylic acid 1,2-diisopropyl ester
• 英文别名: dipropan-2-yl 1-(cyclohexanecarbonyl)hydrazine-1,2-dicarboxylate；diisopropyl 1-(cyclohexanecarbonyl)hydrazine-1,2-dicarboxylate；propan-2-yl N-(cyclohexanecarbonyl)-N-(propan-2-yloxycarbonylamino)carbamate
• 化学式: C₁₅H₂₆N₂O₅
• 分子量: 314.382
• InChiKey: XGQFHFUDIMAQEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-cyclohexylcarbonyl-1,2-hydrazinedicarboxylic acid 1,2-diisopropyl ester 在 盐酸羟胺 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 环己烷羧肟酸
  参考文献：
  名称：

  醛由光有机催化一锅合成异羟肟酸

  摘要：

  描述了一种有效的一锅法从醛和羟胺合成异羟肟酸的方法。快速，可见光介导的偶氮二羧酸二烷基酯的无金属加氢酰化反应用于随后添加盐酸羟胺的过程。在该反应中使用了一系列脂族和芳族醛，以高产率或优异产率得到异羟肟酸。在抗癌药伏立诺他的合成中证明了当前方法的应用。

  DOI：

  10.1002/chem.201600333
• 作为产物：
  描述：

  diisopropyl (E)-azodicarboxylate 、 环己烷基甲醛 在 dirhodium tetraacetate 作用下， 以 乙酸乙酯 为溶剂， 反应 48.0h， 以81%的产率得到1-cyclohexylcarbonyl-1,2-hydrazinedicarboxylic acid 1,2-diisopropyl ester
  参考文献：
  名称：

  偶氮二羧酸盐对过渡金属催化醛的CH活化

  摘要：

  在温和的条件下，乙酸铑催化醛与N N键的活化形式之间的加氢酰化反应，从而可以有效地获得各种肼基酰亚胺。在末端和内部位置均具有不饱和醛的情况下，相对于烯型反应，醛类CH活化具有良好的选择性。

  DOI：

  10.1021/jo035456o

文献信息

• Metal-free, hydroacylation of CC and NN bonds via aerobic C–H activation of aldehydes, and reaction of the products thereof
  作者：Vijay Chudasama、Ahmed R. Akhbar、Karim A. Bahou、Richard J. Fitzmaurice、Stephen Caddick

  DOI：10.1039/c3ob41632a

  日期：——

  In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various CC and NN acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto-sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.

  在本报告中，我们详细评估了使用需氧起始、不含金属的氢酰化方法，将多种CC和NN受体分子与广泛范围的醛进行反应的情况。我们所开发的有氧活化条件与之前的氢酰化条件形成鲜明对比，后者倾向于使用过渡金属、需要热或光化学分解的过氧化物，或者N-杂环卡宾。这些温和的条件使得许多涉及敏感反应物的反应得以进行，或许最为重要的是，能够让α-功能化的手性醛在基于自由基的氢酰化反应中完全保持光学纯度。我们还展示了所得氢酰化产物如何转化成其他有用的中间体，例如γ-酮-磺酰胺、磺内酰胺、磺内酯、环状N-磺酰亚胺和酰胺。
• One-Pot Amide Bond Formation from Aldehydes and Amines via a Photoorganocatalytic Activation of Aldehydes
  作者：Giorgos N. Papadopoulos、Christoforos G. Kokotos

  DOI：10.1021/acs.joc.6b00488

  日期：2016.8.19

  environmentally friendly synthesis of amides from aldehydes and amines is described. Initially, a photoorganocatalytic reaction of aldehydes with di-isopropyl azodicarboxylate leads to an intermediate carbonyl imide, which can react with a variety of amines to afford the desired amides. The initial visible light-mediated activation of a variety of monosubstituted or disubstituted aldehydes is usually fast,

  描述了一种由醛和胺温和，一锅又环保的酰胺合成方法。最初，醛与偶氮二异丙基二异丙酯的光有机催化反应产生中间体羰基酰亚胺，该中间体可与多种胺反应以提供所需的酰胺。各种单取代或双取代醛的初始可见光介导的活化通常很快，发生在几个小时内。在光催化反应之后，在室温下添加伯胺或在高温下添加仲胺导致相应的酰胺从中等收率到优异的收率而没有差向异构化。该方法学被用于合成抗抑郁和社交焦虑症药物莫氯贝胺。
• A Practical and Highly Efficient Hydroacylation Reaction of Azodicarboxylates with Aldehydes in Water
  作者：Allan Headley、Bukuo Ni、Qianying Zhang、Erica Parker

  DOI：10.1055/s-0030-1258056

  日期：2010.10

  The very efficient hydroacylation reaction of azodicarboxylates, with various aldehydes, was carried successfully out at room temperature in water without the use of a catalyst to obtain a variety of hydrazine imide products in high yields. A wide range of aldehydes, including aliphatic and aromatic compounds, was considered, and the reaction is believed to proceed via a radical mechanism, in which

  偶氮二羧酸酯与各种醛的非常有效的加氢酰化反应在室温下在水中成功进行，无需使用催化剂，以高产率获得各种肼酰亚胺产物。考虑了多种醛，包括脂肪族和芳香族化合物，并且该反应被认为是通过自由基机制进行的，其中水在稳定自由基中间体方面起着不可或缺的作用。
• Visible-Light-Mediated Catalytic Hydroacylation of Dialkyl Azodicarboxylates by Graphite Flakes
  作者：Giorgos S. Koutoulogenis、Maroula G. Kokotou、Errika Voutyritsa、Dimitris Limnios、Christoforos G. Kokotos

  DOI：10.1021/acs.orglett.7b00519

  日期：2017.4.7

  A nova and efficient Metal-free catalyted hydroacylation of dialkyl azodicarboxylates is reported. Graphite flakes were found to be the most efficient catalyst among other carbon-based materials to prothote this reaction. This unprecedented catalytic activity can be expanded into a wide substrate scope of aliphatic aldehydes bearing various functional groups, leading to the corresponding products in good to excellent yields.
• Efficient C–H/C–N and C–H/C–CO–N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate
  作者：Ilhyong Ryu、Akihiro Tani、Takahide Fukuyama、Davide Ravelli、Sara Montanaro、Maurizio Fagnoni

  DOI：10.1021/ol401061v

  日期：2013.5.17

  Tetrabutylammonium decatungstate (TBADT) accelerated the addition of C-H bonds to the N=N double bond of diisopropyl azodicarboxylate (DIAD) under irradiation conditions. The photoinduced three-component coupling between cyclic alkanes, CO, and DIAD was also achieved to give the corresponding acyl hydrazides.