(+)-N,N'-bis(ethoxycarbonyl)-2-hydrazino-2-phenyl-propionaldehyde

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-N,N'-bis(ethoxycarbonyl)-2-hydrazino-2-phenyl-propionaldehyde
• 英文别名: (R)-2-[N,N'-bis(ethoxycarbonyl)hydrazino]-2-phenylpropionaldehyde；(R)-diethyl 1-(1-oxo-2-phenylpropan-2-yl)hydrazine-1,2-dicarboxylate；(-)-2-[N,N'-bis(ethoxycarbonyl)hydrazino]-2-phenyl-propionaldehyde；ethyl N-(ethoxycarbonylamino)-N-[(2R)-1-oxo-2-phenylpropan-2-yl]carbamate
• 化学式: C₁₅H₂₀N₂O₅
• 分子量: 308.334
• InChiKey: METMMBGRAINDBT-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  (+)-N,N'-bis(ethoxycarbonyl)-2-hydrazino-2-phenyl-propionaldehyde 在 sodium hydroxide 、 sodium tetrahydroborate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 (-)-3-ethoxycarbonylamino-4-methyl-4-phenyl-oxazolidin-2-one
  参考文献：
  名称：

  脯氨酸催化支化醛的不对称胺化

  摘要：

  已经提出了一种有效获取构型稳定的 α,α-二取代 α-氨基醛、恶唑烷酮和 α-氨基酸的方法。从简单易得的外消旋醛开始，使用偶氮二羧酸盐作为氮源以高达 86% ee 和中等至极好的收率获得 α-胺化产物。这些产物可以进一步转化为相应的 α-氨基醇，并且取决于偶氮二羧酸酯的残留物和反应条件，转化为恶唑烷酮。另一方面，在温和条件下向羧酸的氧化和酰肼键的断裂揭示了游离的 α-烷基化苯基甘氨酸衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200600654
• 作为产物：
  描述：

  2-苯基丙醛 、 偶氮二甲酸二乙酯 在 三氟乙酸 、 (1R,2R)-1-(1',8'-naphthalimido)-2-aminocyclohexane 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 5.0h， 以96%的产率得到(+)-N,N'-bis(ethoxycarbonyl)-2-hydrazino-2-phenyl-propionaldehyde
  参考文献：
  名称：

  第四立体中心的构建：单酰亚胺取代的环己烷-1，2-二胺催化的支链醛的不对称α-胺化

  摘要：

  据报道，由手性酰亚胺单取代的1,2-二胺衍生物催化的支链醛类的高效对映选择性α-胺化可提供优良的产率（高达99％）和对映选择性（高达ee的97％）的四级立体异构中心。手性25：668–672，2013年。©2013 Wiley Periodicals，Inc

  DOI：

  10.1002/chir.22203

文献信息

• Effective construction of quaternary stereocenters by highly enantioselective α-amination of branched aldehydes
  作者：Ji-Ya Fu、Xiao-Ying Xu、Yan-Chun Li、Qing-Chun Huang、Li-Xin Wang

  DOI：10.1039/c0ob00406e

  日期：——

  A highly efficient enantioselective α-amination of branched aldehydes with azadicarboxylates promoted by chiral proline-derived amide thiourea bifunctional catalysts was developed for the first time, affording the adducts bearing quaternary stereogenic centers with excellent yields (up to 99%) and enantioselectivities (up to 97% ee).

  首次开发了由手性脯氨酸衍生的酰胺硫脲双功能催化剂促进的氮杂二羧酸与支链醛的高效对映选择性α-胺化反应，使带有季立体中心的加合物具有优异的收率（高达99％）和对映选择性（高达97％ee）。
• Chiral α-Arylethanamines: An Organocatalyst for the Enantioselective α-Amination of Branched Aldehydes
  作者：Ji-Ya Fu、Qi-Lin Wang、Lin Peng、Yong-Yuan Gui、Fan Wang、Fang Tian、Xiao-Ying Xu、Li-Xin Wang

  DOI：10.1002/ejoc.201201701

  日期：2013.5

  α-Arylethanamines were investigated as organocatalysts for the α-amination of branched aldehydes with azodicarboxylates. Optimization identified (R)-1-(1-naphthyl)ethanamine (1g) as an effective and enantioselective organocatalyst; multifunctional chiral quaternary amino aldehydes were successfully obtained in excellent yields (up to 99 %) and with excellent enantioselectivities (up to 98 % ee).

  α-芳基乙醇胺被研究作为有机催化剂用于支链醛与偶氮二羧酸酯的 α-胺化。优化确定 (R)-1-(1-萘基) 乙胺 (1g) 是一种有效的对映选择性有机催化剂；以优异的产率（高达 99 %）和优异的对映选择性（高达 98 % ee）成功获得了多功能手性季氨基醛。
• Proline-catalysed asymmetric amination of α,α-disubstituted aldehydes: synthesis of configurationally stable enantioenriched α-aminoaldehydes
  作者：Henning Vogt、Sylvia Vanderheiden、Stefan Bräse

  DOI：10.1039/b305465a

  日期：——

  Proline-catalysed amination of α,α-disubstituted racemic aldehydes with azodicarboxylates proceeds smoothly to give configurationally stable scalemic aldehydes and oxazolidinones in up to 86% ee.

  脯氨酰催化的α,α-二取代外消旋醛与叠氮羧酸酯的氨化反应顺利进行，产生构型稳定的非外消旋醛和噁唑啉酮，最高可达86%的ee值。
• β-tert-Butyl aspartate as an organocatalyst for the asymmetric α-amination of α,α-disubstituted aldehydes
  作者：Alexis Theodorou、Giorgos N. Papadopoulos、Christoforos G. Kokotos

  DOI：10.1016/j.tet.2013.04.103

  日期：2013.7

  The enantioselective alpha-amination reaction of alpha,alpha-disubstituted aldehydes can lead to a variety of enantioenriched amino aldehydes, amino alcohols, and amino acids. After screening a variety of amino acids and their derivatives, we identified a cheap, simple, commercially available aspartic acid derivative that can catalyze efficiently the reaction between alpha,alpha-disubstituted aldehydes and dialkyl azodicarboxylates. The reaction proceeds smoothly leading to the corresponding alpha-aminated adducts in moderate to quantitative yields and moderate to high enantioselectivities (up to 96% ee). Finally, the conversion of these adducts to alpha,alpha-disubstituted quaternary amino acids is also described. 2013 Elsevier Ltd. All rights reserved.
• Primary amine catalyzed electrophilic amination of α,α-disubstituted aldehydes
  作者：Alaric Desmarchelier、Hasret Yalgin、Vincent Coeffard、Xavier Moreau、Christine Greck

  DOI：10.1016/j.tetlet.2011.06.063

  日期：2011.8

  Organocatalytic alpha-amination of alpha,alpha-disubstituted aldehydes promoted by 9-amino-(9-deoxy)-epi-quinine is described. alpha-Hydrazino aldehydes bearing a quaternary stereogenic center are obtained in good to excellent yields and enantioselectivities. (C) 2011 Elsevier Ltd. All rights reserved.