(R_p)-tert-butyl(hydroxymethyl)(phenyl)phosphineborane | 1345347-22-9

• 英文名称: (R_p)-tert-butyl(hydroxymethyl)(phenyl)phosphineborane
• 英文别名: tert-butyl(hydroxymethyl)phenylphosphine borane；(S_p)-tert-butyl(hydroxymethyl)(phenyl)phosphineborane
• CAS: 1345347-22-9；565232-54-4；565450-04-6
• 化学式: C₁₁H₂₀BOP
• 分子量: 210.064
• InChiKey: QOMQKTSYMVAMFH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.36
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (R_p)-tert-butyl(hydroxymethyl)(phenyl)phosphineborane 在 辛烯 、 sulfur 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  脂肪酶介导的手性有机磷P-硼烷的立体选择性转化：烷氧基（羟甲基）苯基膦P-硼烷的绝对构型的修订

  摘要：

  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。

  DOI：

  10.1016/j.tetasy.2011.08.024
• 作为产物：
  描述：

  tert-Butylphenylphosphine oxide 反应 7.0h， 生成 (R_p)-tert-butyl(hydroxymethyl)(phenyl)phosphineborane
  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

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。
• Novel Synthesis of P-Chiral Hydroxymethylphosphine–Boranes through Lipase-Catalyzed Optical Resolution
  作者：Kosei Shioji、Yoshimitsu Kurauchi、Kentaro Okuma

  DOI：10.1246/bcsj.76.833

  日期：2003.4

  A novel approach toward the lipase-catalyzed acylation of alkyl(1-hydroxymethyl)phosphine–boranes was achieved. Up to 99% of enantiomerically enriched phosphine–boranes was obtained by using lipase AK and CAL.

  实现了脂肪酶催化烷基（1-羟甲基）膦硼烷酰化的新方法。通过使用脂肪酶 AK 和 CAL，获得了高达 99% 对映体富集的膦硼烷。
• 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。
• Reduction of Functionalized Tertiary Phosphine Oxides with BH₃
  作者：Sylwia Sowa、Marek Stankevič、Anna Szmigielska、Hanna Małuszyńska、Anna E. Kozioł、K. Michał Pietrusiewicz

  DOI：10.1021/jo502623g

  日期：2015.2.6

  A direct stereoselective conversion of tertiary hydroxyalkylphosphine oxides to the corresponding tertiary hydroxyalkylphosphineboranes involving facile reduction of the P=O bond by BH3 under mild conditions has been developed. The unprecedented facility of reduction of the strong P=O bond by BH3, a mild reducing agent, has been achieved through an intramolecular P=O center dot center dot center dot B complexation directed by proximal alpha- or beta-hydroxy groups present in the phosphine oxide structures. As established by two chemical correlations, the developed transformation of hydroxyalkylphosphine oxides into hydroxyalkylphosphine-boranes takes place with complete inversion of configuration at P.