(S_p)-tert-butyl(hydroxymethyl)(phenyl)phosphine oxide | 249931-33-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S_p)-tert-butyl(hydroxymethyl)(phenyl)phosphine oxide
• 英文别名: (+)-(S)-hydroxymethyl-t-butylphenylphosphine oxide；(S)-t-butyl(hydroxymethyl)phenylphosphine oxide；[Tert-butyl(phenyl)phosphoryl]methanol
• CAS: 249931-33-7
• 化学式: C₁₁H₁₇O₂P
• 分子量: 212.229
• InChiKey: GZUQSBLQZUAVAF-CQSZACIVSA-N

物化性质

• 沸点：
  374.7±34.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S_p)-tert-butyl(hydroxymethyl)(phenyl)phosphine oxide 在 三正丁基氢锡 、 三甲胺盐酸盐 、 三乙胺 、 sodium iodide 作用下， 以 乙二醇二甲醚 、 甲苯 为溶剂， 生成 (S)-(-)-tert-butylmethylphenylphosphine oxide
  参考文献：
  名称：

  Lipase-catalyzed kinetic resolution of P-chiral phosphorus compounds: enantiopreference of Pseudomonas lipase and Candida antarctica lipase

  摘要：

  Optically active 1-hydroxymethylalkylphenylphosphine oxides la-c were prepared by Pseudomonas fluorescens lipase (lipase AK) and Candida antarctica lipase (CAL)-catalyzed optical resolution. Lipase AK-catalyzed resolution of tert-butyl derivative 1c showed R-selectivity, whereas CAL preferred the S-enantiomer. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01349-1
• 作为产物：
  描述：

  ethyl Phenylphosphinate 在 Psudomonas fluorescens lipase 3 A molecular sieve 作用下， 以 四氢呋喃 、 异丙醚 为溶剂， 反应 7.0h， 生成 (S_p)-tert-butyl(hydroxymethyl)(phenyl)phosphine oxide
  参考文献：
  名称：

  Lipase-catalyzed kinetic resolution of P-chiral phosphorus compounds: enantiopreference of Pseudomonas lipase and Candida antarctica lipase

  摘要：

  Optically active 1-hydroxymethylalkylphenylphosphine oxides la-c were prepared by Pseudomonas fluorescens lipase (lipase AK) and Candida antarctica lipase (CAL)-catalyzed optical resolution. Lipase AK-catalyzed resolution of tert-butyl derivative 1c showed R-selectivity, whereas CAL preferred the S-enantiomer. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01349-1

文献信息

• Stereospecific Synthesis of α- and β-Hydroxyalkyl P-Stereogenic Phosphine-Boranes and Functionalized Derivatives: Evidence of the PO Activation in the BH₃-Mediated Reduction
  作者：Sébastien Lemouzy、Duc Hanh Nguyen、Valentine Camy、Marion Jean、David Gatineau、Laurent Giordano、Jean-Valère Naubron、Nicolas Vanthuyne、Damien Hérault、Gérard Buono

  DOI：10.1002/chem.201502647

  日期：2015.10.26

  Access to hydroxy‐functionalized P‐chiral phosphine–boranes has become an important field in the synthesis of P‐stereogenic compounds used as ligands in asymmetric catalysis. A family of optically pure α and β‐hydroxyalkyl tertiary phosphine–boranes has been prepared by using a three‐step procedure from readily accessible enantiopure adamantylphosphinate, obtained by semi‐preparative HPLC on multigram

  在不对称催化中用作配体的P-立体异构化合物的合成中，获得羟基官能化的P-手性膦-硼烷已成为重要领域。使用易于制备的对映纯金刚烷基次膦酸酯，可通过三步法从多级克制的半制备性HPLC中获得，制备一族光学纯的α和β-羟烷基叔膦-硼烷。首先，两步一锅法转化得到对映体纯的羟烷基叔膦氧化物，具有良好的收率和对映选择性。第三步，BH 3介导的还原，可以形成具有优异立体特异性的所需膦基硼烷。这种还原的机理研究提供了新的证据，阐明了侧链羟基的关键作用以及随后硼原子激活P activationO键的作用。
• New procedures for the resolution of chiral tert-butylphenylphosphine oxide and some of its reactions
  作者：Józef Drabowicz、Piotr Łyżwa、Jan Omelańczuk、K.Michał Pietrusiewicz、Marian Mikołajczyk

  DOI：10.1016/s0957-4166(99)00264-5

  日期：1999.7

  diastereoisomeric complexes with (+)-(R)-1,1′-binaphthalene-2,2′-diol and (+)-(S)-mandelic acid. With the latter complexing agent, separation of the essentially enantiopure (−)-(S)-enantiomer was achieved in a single complexation process. Addition of paraformaldehyde to this enantiomer gave α-hydroxymethyl-t-butylphenylphosphine oxide with high stereoselectivity and retention of configuration at phosphorus

  外消旋的叔丁基苯基氧化膦是通过与（+）-（R）-1,1'-双萘-2,2'-二醇和（+）-（S）-扁桃酸的非对映异构体配合物拆分而得到的。使用后一种络合剂，可以在单个络合过程中分离出基本对映体（-）-（S）-对映体。向该对映异构体中添加多聚甲醛可得到具有高立体选择性和磷保持结构的α-羟甲基-叔丁基苯基膦氧化物，同时它与溴乙酸甲酯在甲醇/甲醇钠中的反应导致形成叔丁基苯基次膦酸甲酯，并在磷下转化。
• IMIDAZOLE GROUP-CONTAINING PHOSPHORUS COMPOUNDS
  申请人：Hofmann Peter

  公开号：US20100317866A1

  公开（公告）日：2010-12-16

  The present invention relates to phosphorus compounds containing imidazole groups, to optically active ligands prepared using them, to transition metal complexes which comprise such ligands, and to catalysts which comprise such transition metal complexes. The present invention further relates to the particular processes for preparing the phosphorus compounds, the optically active ligands, the transition metal complexes and the catalysts, and also to the use of the catalysts for organic transformation reactions.

  本发明涉及含有咪唑基的磷化合物，以及使用它们制备的光学活性配体，包括这样的配体的过渡金属配合物和包含这样的过渡金属配合物的催化剂。本发明还涉及用于制备磷化合物、光学活性配体、过渡金属配合物和催化剂的特定过程，以及使用催化剂进行有机转化反应的用途。
• Lipase-mediated stereoselective transformations of chiral organophosphorus P-boranes revisited: revision of the absolute configuration of alkoxy(hydroxymethyl)phenylphosphine P-boranes
  作者：Małgorzata Kwiatkowska、Grzegorz Krasiński、Marek Cypryk、Tomasz Cierpiał、Piotr Kiełbasiński

  DOI：10.1016/j.tetasy.2011.08.024

  日期：2011.7

  moderate stereoselectivity to give both the unreacted substrates and their O-acetyl derivatives. The absolute configurations of the products, which were earlier ascribed on the basis of the stereoselective reduction of the corresponding phosphine oxides with borane and comparison with the literature data concerning bicyclic phosphine oxides, were disputed by theoretical calculation. Some additional

  脂肪酶促进的一系列烷氧基（羟甲基）苯基膦P-硼烷的动力学拆分以适度的立体选择性进行，从而得到未反应的底物和它们的O-乙酰基衍生物。产物的绝对构型在理论计算上受到争议，该产物的绝对构型先前是由于用硼烷对相应的膦氧化物进行了立体选择性还原并与有关双环膦氧化物的文献数据进行了比较。进行了一些其他的研究，包括理论计算和更精确的化学相关性，证明无环氧化膦的硼烷还原反应是在磷中心进行构型反转的，因此，先前对绝对构型的分配是不正确的。在此基础上，最终确定了酶促反应的立体化学。