(S)-dimethyl (1-phenylethyl)phosphonate | 130696-26-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: (S)-dimethyl (1-phenylethyl)phosphonate
• 英文别名: [(1S)-1-dimethoxyphosphorylethyl]benzene
• CAS: 130696-26-3
• 化学式: C₁₀H₁₅O₃P
• 分子量: 214.201
• InChiKey: UZTLHSNIHBRWEG-VIFPVBQESA-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：

  (2S,6S)-2-benzyl-3-tert-butyl-6-methyl-1,3,2lambda5-oxazaphosphinane 2-oxide 在 盐酸 、 叔丁基锂 作用下， 生成 (S)-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。
• Diastereoselective alkylations of chiral, phosphorus-stabilized carbanions: <i>N</i>-alkyl substituent effects in <i>P</i>-alkyl-1,3,2-diazaphosphorinane 2-oxides
  作者：Scott E Denmark、Jung-Ho Kim

  DOI：10.1139/v99-251

  日期：2000.6.1

  A systematic study of the diastereoselective alkylation of anions derived from racemic N-substituted P-alkyl 1,3,2-diazaphosphorinane 2-oxides was carried out with variation of the N-substituent. High diastereoselectivity for the methylation of a P-benzyl anion has been achieved with N-neopentyl derivative 5d. Similarly, a P-ethyl anion derived from N-neopentyl derivative 6d showed high diastereoselectivity

  对衍生自外消旋 N-取代的 P-烷基 1,3,2-二氮杂膦烷 2-氧化物的阴离子的非对映选择性烷基化进行了系统研究，其中 N-取代基发生了变化。N-新戊基衍生物 5d 已实现对 P-苄基阴离子甲基化的高非对映选择性。类似地，衍生自 N-新戊基衍生物 6d 的 P-乙基阴离子在苄基化时显示出高非对映选择性。讨论了观察到的 P-乙基和 P-苄基阴离子对各种 N-烷基取代基的烷基化非对映选择性的差异。关键词：膦酰胺稳定的碳负离子，烷基化，不对称，立体选择性，有机锂。
• Ni-Catalyzed Asymmetric Hydrogenation of α-Substituted α,β-Unsaturated Phosphine Oxides/Phosphonates/Phosphoric Acids
  作者：Xuanliang Yang、Gang Liu、Xun Xiang、Dezheng Xie、Jinyu Han、Zhengyu Han、Xiu-Qin Dong

  DOI：10.1021/acs.orglett.2c04105

  日期：2023.2.10

  Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of α-substituted α,β-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral α-substituted phosphines hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%–99% yields, 84%−>99% ee). This method features a cheap transition metal

  成功开发了Ni/( S , S )-Ph-BPE催化的α-取代α,β-不饱和膦氧化物/膦酸酯/磷酸的高效不对称加氢反应，并获得了多种手性α-取代膦加氢产物获得普遍高产率和出色的对映选择性控制（92%–99% 产率，84%−>99% ee）。该方法具有廉价的过渡金属镍催化体系、高官能团耐受性、广泛的底物范围通用性和优异的对映选择性。根据氘标记实验的结果，为这种不对称氢化提出了一个似是而非的催化循环。
• 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.