ethyl allylphosphinate | 173781-45-8

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: ethyl allylphosphinate
• 英文别名: ethyl allyl-H-phosphinate；3-[Ethoxy(oxido)phosphaniumyl]prop-1-ene；3-[ethoxy(oxido)phosphaniumyl]prop-1-ene
• CAS: 173781-45-8
• 化学式: C₅H₁₁O₂P
• 分子量: 134.115
• InChiKey: BGFHICLSSBIRCW-UHFFFAOYSA-N

物化性质

• 沸点：
  162.0±33.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl allylphosphinate 在 palladium dihydroxide lithium aluminium tetrahydride 、 氢气 、 S-1,1'-联-2-萘酚 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  β-氨基-α-羟基（烯丙基）次膦酸酯的立体选择性合成及其在合成次膦酰肽结构单元中的应用

  摘要：

  在 (S)-ALB 存在下，N,N-二苄基-α-氨基醛与烯丙基次膦酸乙酯的氢膦酰化以高非对映选择性提供抗-β-氨基-α-羟基（烯丙基）次膦酸。氢膦酰化产物被转化为潜在有用的过渡态模拟物，用于二肽的水解。

  DOI：

  10.1055/s-2002-33529
• 作为产物：
  描述：

  allyl-(1,1-diethoxy-ethyl)-phosphinic acid ethyl ester 在 三甲基氯硅烷 作用下， 以 乙醇 、 氯仿 为溶剂， 生成 ethyl allylphosphinate
  参考文献：
  名称：

  1,1-Diethoxyethylphosphinates and phosphonites. Intermediates for the synthesis of functional phosphorus acids

  摘要：

  Masked hypophosphorous and methanephosphonous acid synthons have been developed which provide functional phosphonous esters after mild deprotection.

  DOI：

  10.1016/0040-4039(95)01992-q

文献信息

• DBU-promoted alkylation of alkyl phosphinates and H-phosphonates
  作者：Laurent Gavara、Christelle Petit、Jean-Luc Montchamp

  DOI：10.1016/j.tetlet.2012.07.019

  日期：2012.9

  phosphinates and some H-phosphonate diesters is promoted by the base DBU. Only more reactive alkyl halides react in preparatively useful yields. However, the method provides easy access to important H-phosphinate building blocks, without the need for a protecting group strategy or metal catalysts. The reaction is conveniently conducted at, or below, room temperature. The preparation of methyl-H-phosphinate

  DBU碱促进烷基次膦酸酯和一些H-膦酸酯二酯的烷基化。只有更多的反应性烷基卤化物以制备有用的产率反应。但是，该方法无需重要的保护基策略或金属催化剂即可轻松获得重要的H-次膦酸酯结构单元。该反应方便地在室温或低于室温下进行。甲基的制备ħ -phosphinate酯是特别令人感兴趣的，因为它避免了以往更普遍使用methyldichlorophosphine MePCl的2。
• Facile P,N-heterocycle synthesis via tandem aminomethylation–cyclization of H-phosphinate building blocks
  作者：Clémence Queffélec、Jean-Luc Montchamp

  DOI：10.1039/b917428a

  日期：——

  Various heterocycles containing phosphorus and nitrogen are easily synthesized from readily available H-phosphinate building blocks. Aminomethylation of these H-phosphinates is followed by in situ cyclization through substitution or cross-coupling to produce novel heterocycles in moderate to good yields.

  含磷和氮的多种杂环化合物能够容易地从易得的H-膦酸酯砌块合成。对这些H-膦酸酯进行胺甲基化后，通过取代或交叉耦合进行原位环化，以中等至良好的产率得到新型杂环化合物。
• Direct Monoalkylation of Alkyl Phosphinates to Access H-Phosphinic Acid Esters
  作者：Jean-Luc Montchamp、Isabelle Abrunhosa-Thomas、Patrice Ribière、Alicia C. Adcock

  DOI：10.1055/s-2005-924768

  日期：——

  Simple alkyl phosphinates prepared by the silicate esterification method can be alkylated under Barbier-like conditions with butyl lithium at -78 °C followed by warming to room temperature. The method is limited to the more reactive electrophile such as allylic bromides and alkyl iodides. With these electrophiles good yields of H-phosphinic acid esters are generally obtained in a straightforward manner

  通过硅酸酯化方法制备的简单烷基次膦酸盐可以在类似巴比尔的条件下与丁基锂在 -78 °C 下烷基化，然后升温至室温。该方法仅限于反应性更强的亲电子试剂，例如烯丙基溴化物和烷基碘化物。使用这些亲电子试剂，通常以简单的方式获得高产率的 H-次膦酸酯。
• Diastereoselective synthesis of β-substituted α-hydroxyphosphinates through hydrophosphinylation of α-heteroatom-substituted aldehydes
  作者：Takehiro Yamagishi、Takanori Kusano、Babak Kaboudin、Tsutomu Yokomatsu、Chiseko Sakuma、Shiroshi Shibuya

  DOI：10.1016/s0040-4020(02)01629-0

  日期：2003.2

  The diastereoselective synthesis of β-substituted α-hydroxyphosphinates was achieved by hydrophosphinylation of α-oxy aldehydes and α-amino aldehydes with ethyl allylphosphinate catalyzed by lithium phenoxide.

  β-取代的α-羟基次膦酸酯的非对映选择性合成是通过苯氧基锂催化的烯丙基次膦酸乙酯对α-氧基醛和α-氨基醛进行氢膦酰化而实现的。
• Stereoselective Synthesis of β-Amino-α-hydroxy(allyl)phosphinates and an Application to the Synthesis of a Building Block for Phosphinyl Peptides
  作者：Tsutomu Yokomatsu、Takehiro Yamagishi、Takanori Kusano、Shiroshi Shibuya

  DOI：10.1055/s-2002-33529

  日期：——

  Hydrophosphinylation of N,N-dibenzyl-α-amino aldehydes with ethyl allylphosphinate in the presence of (S)-ALB afforded anti-β-amino-a-hydroxy(allyl)phosphinates in high diastereoselectivity. The hydrophosphinylation product was transformed to a potentially useful transition state mimic for hydrolysis of dipeptides.

  在 (S)-ALB 存在下，N,N-二苄基-α-氨基醛与烯丙基次膦酸乙酯的氢膦酰化以高非对映选择性提供抗-β-氨基-α-羟基（烯丙基）次膦酸。氢膦酰化产物被转化为潜在有用的过渡态模拟物，用于二肽的水解。