(R)-dimethyl (1-phenylethyl)phosphonate | 130696-25-2

• 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: (R)-dimethyl (1-phenylethyl)phosphonate
• 英文别名: (1R)-(+)-1-phenethyl dimethylphosphonate；(r)-Dimethyl 1-phenylethyl-phosphonate；[(1R)-1-dimethoxyphosphorylethyl]benzene
• CAS: 130696-25-2
• 化学式: C₁₀H₁₅O₃P
• 分子量: 214.201
• InChiKey: UZTLHSNIHBRWEG-SECBINFHSA-N

物化性质

• 沸点：
  295.9±19.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  benzylphosphonic dichloride 在 盐酸 、 叔丁基锂 、 三乙胺 作用下， 生成 (R)-dimethyl (1-phenylethyl)phosphonate
  参考文献：
  名称：

  Stereoselective alkylations of chiral, phosphorus-stabilized benzylic carbanions

  摘要：

  DOI：

  10.1021/jo00311a003

文献信息

• The asymmetric synthesis of α-substituted α-methyl and α-phenyl phosphonic acids: Design, carbanion geometry, reactivity and preparative aspects of chiral alkyl bicyclic phosphonamides
  作者：Youssef L. Bennani、Stephen Hanessian

  DOI：10.1016/0040-4020(96)00829-0

  日期：1996.10

  The design, preparation, structural and spectroscopic analyses of topologically unique and enantiomerically pure alkyl phosphonamides are described. In the case of α-ethyl and α-benzyl phosphonamides, the geometry of both the secondary and tertiary carbanions was determined to be planar through deprotonation/deuteration/alkylation experiments. Stereoselective alkylations of such systems proceeded in

  描述了拓扑独特和对映体纯的烷基膦酰胺的设计，制备，结构和光谱分析。在α-乙基和α-苄基膦酰胺的情况下，通过去质子化/氘代/烷基化实验，确定了仲和叔碳负离子的几何形状均为平面。这种系统的立体选择性烷基化以高收率和高非对映选择性进行。水解所得的α，α-烷基膦酰胺，得到具有高对映体纯度的相应的α，α-烷基膦酸。
• Efficient Asymmetric Hydrogenation of α-Acetamidocinnamates through a Simple, Readily Available Monodentate Chiral<i>H</i>-Phosphinate
  作者：Xiang-Bo Wang、Midori Goto、Li-Biao Han

  DOI：10.1002/chem.201304675

  日期：2014.3.24

  An air‐stable, simple (RP)‐mentylbenzylphosphinate, readily available in large quantities, can efficiently induce the rhodium‐catalyzed asymmetric hydrogenation of α‐acetamidocinnamates with high enantioselectivity (up to 99.6 % ee). Intramolecular hydrogen bonding plays an important role in this asymmetric induction.

  空气稳定，简单的（R P）-薄荷基苄基次膦酸酯可以轻松获得，可以高效诱导铑催化的对乙酰氨基二甲酸酯的不对称氢化，对映选择性高（ee高达99.6％）。分子内氢键在这种不对称诱导中起重要作用。
• Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides
  作者：Hanlin Wei、Hao Chen、Jianzhong Chen、Ilya D. Gridnev、Wanbin Zhang

  DOI：10.1002/anie.202214990

  日期：2023.2

  The first efficient Ni-catalyzed asymmetric hydrogenation of terminal olefins using H2 was developed, affording chiral ethylphosphine products with up to 99 % yield, 96 % ee and 1000 S/C (substrate/catalyst). The calculation and experimental mechanism study indicate that the two added hydrogen atoms of the product originate from H2 and the reaction proceeds through a NiII rather than Ni0 cyclic process

  开发了第一个使用 H 2对末端烯烃进行有效的镍催化不对称氢化反应，提供了高达 99% 收率、96% ee 和 1000 S/C（底物/催化剂）的手性乙基膦产物。计算和实验机理研究表明，产物中加入的两个氢原子来源于H 2，反应通过Ni II而不是Ni 0循环过程进行。
• CAMDOL-enabled diastereoselective synthesis of α-substituted phosphonates
  作者：Yu Huang、Yulong Zhang、Li Pan、Qian Wu、Ning Li、Enxue Shi、Junhua Xiao

  DOI：10.1039/d3cc05436e

  日期：——

  we present a highly diastereoselective synthesis of α-substituted phosphonates via the unique CAMDOL-derived P-substrates by an efficient sequential deprotonation with LiHMDS and alkylation/arylation with RI. A wide range of 30 structurally diverse α-substituted phosphonate products, including the well-known P-analogues of naproxen and ibuprofen, were thus afforded conveniently in up to 92% yields

  对映体纯α-取代膦酸广泛用作药物、农药和配体。尽管已经研究了许多合成方法，但通过使用可回收的手性助剂来精确构建P-相邻手性叔碳中心是传统的，并且仍然是迄今为止最可靠和实用的合成方法之一。在此，我们通过独特的 CAMDOL 衍生的 P-底物，通过 LiHMDS 的有效连续去质子化和 RI 的烷基化/芳基化，提出了 α-取代膦酸酯的高度非对映选择性合成。因此，可以方便地以高达 92% 的产率和 99:1 的非对映异构体比例方便地提供 30 种结构多样的 α-取代膦酸酯产品，包括众所周知的萘普生和布洛芬的 P-类似物。在完全回收助剂的情况下，通过简单的酸水解可以很容易地获得相关的手性膦酸。这种支持 CAMDOL 的不对称合成方案与已知的手性诱导方法相比具有比较优势，并且易于获取，并且在磷原子附近提供各种 C-立体中心（包括一些罕见的例子）。
• Alkylations of Chiral, Phosphoryl- and Thiophosphoryl-Stabilized Carbanions
  作者：Scott E. Denmark、Chien-Tien Chen

  DOI：10.1021/ja00153a009

  日期：1995.12

  A general method for the preparation of enantiomerically enriched phosphonic acids and phosphonates with three different a-substitution patterns (aryl, alkyl, and alkoxy) has been developed. Anions derived from enantiomerically enriched thiophosphonamidates (2-thioxo-1,3,2-oxazaphosphorinanes) underwent smooth electrophilic substitutions with excellent diastereoselectivity for both cis and trans stereoisomers. Highly enantioselective synthesis of alpha-alkoxyphosphonates in either antipodal form can be achieved by the employment of highly diastereoselective alkylation with anions derived from the corresponding P-methoxymethyl analogs in the presence of HMPA or PMDTA. Implications for the aggregation states and reactive conformations of the anions are discussed.