(R)-1-phenylethyl diethyl phosphate | 81238-80-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (R)-1-phenylethyl diethyl phosphate
• 英文别名: (R)-(+)-Phosphorsaeure-diethylester-(1-phenylethylester)；diethyl 1-phenylethyl phosphate；(R)-diethyl (1-phenylethyl) phosphate；diethyl [(1R)-1-phenylethyl] phosphate
• CAS: 81238-80-4
• 化学式: C₁₂H₁₉O₄P
• 分子量: 258.254
• InChiKey: KEHCTXDLIGSVEI-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-1-phenylethyl diethyl phosphate 在 正丁基锂 、 正己烷 、 二异丙胺 作用下， 以 甲苯 为溶剂， 以84%的产率得到(S)-(-)-(1-Hydroxy-1-phenylethyl)phosphonsaeurediethylester
  参考文献：
  名称：

  Hammerschmidt, Friedrich; Voellenkle, Horst, Liebigs Annalen der Chemie, 1986, # 12, p. 2053 - 2064

  摘要：

  DOI：
• 作为产物：
  描述：

  (R)-(+)-1-苯基乙醇 、 氯磷酸二乙酯 在 N-甲基咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以94%的产率得到(R)-1-phenylethyl diethyl phosphate
  参考文献：
  名称：

  二芳基甲基阴离子取代仲苯甲酸磷酸酯

  摘要：

  取代二乙基和二苯基苄基磷酸酯Alk-CH（Ar 1）OP（O）（OR）2（R = Et，Ph; Alk = Me，Et，i- Pr; Ar 1  =芳基），并衍生出阴离子选自Ar 2 CH 2（PH 2 CH 2，9 ħ呫吨和芴）和ñ正丁基锂在-15℃下进行了研究。对于以Me为碱的磷酸盐，磷酸二乙酯可制得Me-CH（Ar 1）CH（Ar 2）2（Ar 1  = 4-卤代，4-CN，4-Me-，2-Me，2-Br- ，3-MeO-苯基和2-萘基）。但是，在Et基团上的不需要的取代与Alk = Et-的磷酸盐竞争我-Pr。幸运的是，相应的磷酸二苯酯干净地进行了所需的取代。两种对映体富集的磷酸盐MeCH（Ph）OP（O）（OEt）2和EtCH（Ph）OP（O）（OPh）2进行了立体化学的完全转化。

  DOI：

  10.1016/j.tet.2019.03.050

文献信息

• Asymmetric Hydrogenation of Enol Phosphinates by Iridium Catalysts Having N,P Ligands
  作者：Pradeep Cheruku、Suresh Gohil、Pher G. Andersson

  DOI：10.1021/ol070325l

  日期：2007.4.1

  [reaction: see text] Enol phosphinates, which are structural analogues of enol acetates, have for the first time been employed as substrates for Ir-catalyzed asymmetric hydrogenation. A number of enol phosphinates have been synthesized and reduced successfully with up to and above 99% ee.

  [反应：见正文]烯醇次膦酸酯是烯醇乙酸酯的结构类似物，首次被用作Ir催化的不对称氢化的底物。已经合成了许多烯醇次膦酸酯，并成功地还原了高达99％ee以上的ee。
• Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates
  作者：Hiroki Miura、Tomoya Toyomasu、Hidenori Nishio、Tetsuya Shishido

  DOI：10.1039/d1cy02085d

  日期：——

  the presence of gold nanoparticles supported on ZrO2 proceeded efficiently under mild reaction conditions to give the corresponding allyl sulfides in excellent yields. ZrO2-Supported gold nanoparticles showed excellent catalytic turnover and reusability. In addition, the C–O bonds of benzyl and propargyl phosphates underwent thioetherification to afford benzyl and propargyl sulfides. The reaction of

  描述了 C(sp 3 )-O 键的金催化硫醚化。在负载在 ZrO 2上的金纳米粒子存在下，烯丙基磷酸酯和硫硅烷的反应在温和的反应条件下有效地进行，从而以优异的产率得到相应的烯丙基硫化物。氧化锆2-支持的金纳米粒子表现出优异的催化周转率和可重复使用性。此外，苄基和炔丙基磷酸酯的 C-O 键经历硫醚化，得到苄基和炔丙基硫化物。光学活性磷酸苄酯的反应以优异的手性转移进行，得到具有高对映体纯度的苄基硫醚。对照实验证实可溶性金物种是磷酸盐 C-O 键有效硫醚化的原因，催化剂的表征表明，负载在 ZrO 2上的金纳米颗粒表面的阳离子金物种可作为高活性催化物种的来源.
• Examining the origin of selectivity in the reaction of racemic alcohols with chiral N-phosphoryl oxazolidinones
  作者：Samuel Crook、Nigel J. Parr、Jonathan Simmons、Simon Jones

  DOI：10.1016/j.tetasy.2014.08.003

  日期：2014.10

  A range of known and novel N-phosphoryl oxazolidinones and imidazolidinones were prepared and screened in the kinetic resolution of a range of racemic magnesium chloroalkoxides. Models are proposed to account for the enantioselectivity achieved based on a combination of chiral relay effects, generation of transient stereochemistry and the structure of the intermediate magnesium alkoxide. (C) 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).
• Stereochemical consequences of the use of chiral N-phosphoryl oxazolidinones in the attempted kinetic resolution of bromomagnesium alkoxides
  作者：Simon Jones、Dimitrios Selitsianos

  DOI：10.1016/j.tetasy.2005.08.025

  日期：2005.9

  A number of chiral N-phosphoryl oxazolidinones have been prepared and evaluated as asymmetric phosphoryl transfer agents with the magnesium alkoxide of 1-phenyl ethanol. The reaction proceeded with little stereo selection, which was shown to be a consequence of the reaction mechanism that occurs with inversion of configuration at phosphorus consistent with in-line attack opposite the leaving group. (C) 2005 Elsevier Ltd. All rights reserved.
• Die Phosphonat-Phosphat- und Phosphat-Phosphonat-Umlagerung und ihre Anwendung, Teil 2: Stereochemie der Phosphonat-Phosphat-Umlagerung am Kohlenstoff am Beispiel der Isomerisierung von (R)-(+)- und (S)-(?)-(1-Hydroxy-1-phenylethyl)-phosphons�ure-diethylester
  作者：F. Hammerschmidt

  DOI：10.1007/bf00814152

  日期：1993.10

  The phosphonate-phosphate-rearrangement of (R)-(+)- and (S)-(-)-6 was investigated at room temperature in various organic solvents and mixtures of organic solvent and of up to 7% of water, using potassium t-butoxide, potassium hydroxide, and DBU as bases. The rearrangement is shown to occur with retention of configuration at carbon. The highest enantiomeric excess (10.7%) for phosphate 8 was observed using a mixture of DMSO and water (100:7) containing DBU as base. Under these conditions the cleavage of phosphonate 6 into acetophenone and phosphite predominates and the yield of phosphate 8 is only 7.7%.