(R)-hydroxymethyl-t-butylphenylphosphine oxide

• 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: (R)-hydroxymethyl-t-butylphenylphosphine oxide
• 英文别名: tert-butyl(hydroxymethyl)-phenylphosphine oxide；(R_p)-tert-butyl(hydroxymethyl)(phenyl)phosphine oxide；(R)-t-butyl(hydroxymethyl)phenylphosphine oxide；[Tert-butyl(phenyl)phosphoryl]methanol
• 化学式: C₁₁H₁₇O₂P
• 分子量: 212.229
• InChiKey: GZUQSBLQZUAVAF-AWEZNQCLSA-N

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：

  (R)-hydroxymethyl-t-butylphenylphosphine oxide 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.08h， 生成 (S_P)-tert-butyl(phenyl)((pyridin-2-ylmethoxy)methyl)phosphine borane
  参考文献：
  名称：

  The Hydroxyalkyl Moiety As a Protecting Group for the Stereospecific Alkylation of Masked Secondary Phosphine-Boranes

  摘要：

  The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) phosphine-boranes under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. The P-alkylation reaction was found to proceed in moderate to very good yields and very high enantiospecificity (es >95%) using a variety of alkyl halides as electrophiles. The configurational stability of the sodium phosphido-borane intermediate was also investigated and allowed a deeper understanding of the reaction mechanism, furnishing secondary phosphine-boranes in moderate yield and enantiopurity.

  DOI：

  10.1021/acs.orglett.5b03450
• 作为产物：
  描述：

  tert-Butylphenylphosphine oxide 在 三乙胺 作用下， 反应 2.0h， 生成 (R)-hydroxymethyl-t-butylphenylphosphine oxide
  参考文献：
  名称：

  拆分手性叔丁基苯基氧化膦及其新反应的新程序1

  摘要：

  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。

  DOI：

  10.1016/s0957-4166(99)00264-5

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。
• Consecutive dynamic resolutions of phosphine oxides
  作者：Felix A. Kortmann、Mu-Chieh Chang、Edwin Otten、Erik P. A. Couzijn、Martin Lutz、Adriaan J. Minnaard

  DOI：10.1039/c3sc52913d

  日期：——

  A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio- and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides.

  结晶诱导的不对称转化（CIAT）涉及到自由基介导的消旋化，从而获得了对映体纯的仲膦氧化物。连续的 CIAT 被用来制备对映体和非对映纯的叔丁基（羟基烷基）苯基膦氧化物。
• 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。
• Theoretical Mechanism Study of BH3‐Mediated Reduction of P‐Stereogenic Hydroxyalkylphosphine Oxides
  作者：Jean‐Marc Mattalia、Guilhem Javierre、Rémy Fortrie、Gérard Buono、Paola Nava、Damien Hérault

  DOI：10.1002/ejoc.202400375

  日期：2024.8.5

  DFT calculations explain the experimentally observed reactivity and stereospecificity for BH3-mediated reductions of P-stereogenic hydroxyalkylphosphine oxides. The proposed computed pathway suggests the formation of a cyclic intermediate and of borohydride as hydride donor.

  DFT 计算解释了实验观察到的 BH 3介导的 P-立体羟烷基氧化膦还原的反应性和立体特异性。所提出的计算途径表明环状中间体和硼氢化物作为氢化物供体的形成。
• Lipase-catalyzed kinetic resolution of P-chiral phosphorus compounds: enantiopreference of Pseudomonas lipase and Candida antarctica lipase
  作者：Kosei Shioji、Yuichiro Ueno、Yoshimitsu Kurauchi、Kentaro Okuma

  DOI：10.1016/s0040-4039(01)01349-1

  日期：2001.9

  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.