[1-((S)-1-Phenyl-ethylcarbamoyl)-ethyl]-phosphonic acid dimethyl ester | 850425-50-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: [1-((S)-1-Phenyl-ethylcarbamoyl)-ethyl]-phosphonic acid dimethyl ester
• 英文别名: 2-dimethoxyphosphoryl-N-[(1S)-1-phenylethyl]propanamide
• CAS: 850425-50-2
• 化学式: C₁₃H₂₀NO₄P
• 分子量: 285.28
• InChiKey: UBVSHXCJOMYKMK-VUWPPUDQSA-N

物化性质

• 沸点：
  452.0±38.0 °C(Predicted)
• 密度：
  1.147±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [1-((S)-1-Phenyl-ethylcarbamoyl)-ethyl]-phosphonic acid dimethyl ester 、 4-氯苯甲醛 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以96%的产率得到(E)-(S)-N-(1-methylbenzyl)-2-methyl-3-(p-chlorophenyl)propenamide
  参考文献：
  名称：

  Practical and Efficient Synthesis of (E)-α,β-Unsaturated Amides Bearing (S)-α-Methylbenzylamine from 2-Phosphonamides via Horner-Wadsworth-Emmons Reaction

  摘要：

  通过Horner-Wadsworth-Emmons反应成功合成了高度立体选择性的(E)-α,β-不饱和酰胺，这些酰胺具有(S)-α-甲基苄胺。起始的膦酰胺可通过三甲基膦酸酯与α-溴酰胺的标准Arbuzov反应在两步中以优异的产率轻松制备。

  DOI：

  10.1055/s-2006-926265
• 作为产物：
  描述：

  (S)-(-)-2-bromo-N-(1-phenylethyl)acetamide 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 [1-((S)-1-Phenyl-ethylcarbamoyl)-ethyl]-phosphonic acid dimethyl ester
  参考文献：
  名称：

  Practical and Efficient Synthesis of (E)-α,β-Unsaturated Amides Bearing (S)-α-Methylbenzylamine from 2-Phosphonamides via Horner-Wadsworth-Emmons Reaction

  摘要：

  通过Horner-Wadsworth-Emmons反应成功合成了高度立体选择性的(E)-α,β-不饱和酰胺，这些酰胺具有(S)-α-甲基苄胺。起始的膦酰胺可通过三甲基膦酸酯与α-溴酰胺的标准Arbuzov反应在两步中以优异的产率轻松制备。

  DOI：

  10.1055/s-2006-926265

文献信息

• Asymmetric alkylation of dimethoxyphosphoryl-N-[1-(S)-α-methylbenzyl]acetamide enolates. Synthesis of both stereoisomers from the same source of chirality by changing the equivalents of LDA
  作者：Mario Ordóñez、Eugenio Hernández-Fernández、Janet Xahuentitla、Carlos Cativiela

  DOI：10.1039/b416616g

  日期：——

  A new methodology has been developed for the synthesis of both stereoisomers from a single chiral source.

  已经开发出一种新方法，可以从单一的手性来源合成两种立体异构体。
• Reversal of diastereoselectivity in the benzylation of the lithium enolates of phosphonopropanoamides by changing the base equivalents
  作者：Mario Ordóñez、Eugenio Hernández-Fernández、Haydée Rojas-Cabrera、Victoria Labastida-Galván

  DOI：10.1016/j.tetasy.2008.11.028

  日期：2008.12

  Phosphonopropanoamides bearing (S)-alpha-methylbenzylamine were easily obtained, and the benzylation of their enolates examined. Surprisingly, a reversal of the pi-facial diastereoselectivity was observed by changing the number of equivalents of the lithium base. Reaction of the lithium enolate obtained using 2.0 equiv of LDA, LiHMDS or LTMP with benzyl bromide afforded the (R,S)-diastereoisomer, whereas the use of >= 2.5 equiv of lithium base gave the (S,S)-diastereoisomer. In contrast, a reversal of diastereoselectivity was not observed with sodium or potassium bases. This reversal is attributed to the formation of aggregates of the enolates. The results presented here provide valuable guidelines to tune the selective preparation of enantiopure compounds from the same source of chirality. (C) 2009 Elsevier Ltd. All rights reserved.
• Reversal Diastereoselectivity in the Benzylation of Phosphonopropanoamides
  作者：Javier Cervantes-González、Selene Lagunas-Rivera、Mario Ordóñez

  DOI：10.1080/10426507.2010.522638

  日期：2011.3.31

  A convenient and efficient preparation of phosphonopropanoamides bearing (S)-1-(1'-naphthyl) ethylamine, (S)-3,3-dimethyl-2-butylamine, and (S)-2-amine-3-methylbutane in good yield has been achieved. The stereochemical outcome of the asymmetric benzylation reaction of their enolates changes dramatically with the LDA equivalents used. The enolization of the phosphopropanoamides with LDA (2 equiv.) followed by the reaction with benzyl bromide gives rise to the (R,S) quaternary phosphonoamides, whereas the (S,S) diastereoisomer can be obtained by enolization with LDA (>= 2.5 equiv.) followed by the addition of benzyl bromide. This method provides access to both diastereoisomers changing only the base equivalents.
• Practical and Efficient Synthesis of (<i>E</i>)-α,β-Unsaturated Amides Bearing (<i>S</i>)-α-Methylbenzylamine from 2-Phosphonamides via Horner-Wadsworth-Emmons Reaction
  作者：Mario Ordóñez、Eugenio Hernández-Fernández、Mario Fernández-Zertuche、Oscar García-Barradas、Omar Muñoz-Muñiz

  DOI：10.1055/s-2006-926265

  日期：——

  The highly stereoselective synthesis of (E)-α,β-unsaturated amides bearing (S)-α-methylbenzylamine was achieved from 2-phosphonamides via Horner-Wadsworth-Emmons reaction. The starting phosphonamides are easily prepared in two steps with ­excellent yields via the standard Arbuzov reaction of trimethyl­phosphite and α-bromoamides.

  通过Horner-Wadsworth-Emmons反应成功合成了高度立体选择性的(E)-α,β-不饱和酰胺，这些酰胺具有(S)-α-甲基苄胺。起始的膦酰胺可通过三甲基膦酸酯与α-溴酰胺的标准Arbuzov反应在两步中以优异的产率轻松制备。