(R)-hydroxymethyl(methyl)phenylphosphine-borane | 281667-51-4

• 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(methyl)phenylphosphine-borane
• 英文别名: (Hydroxymethyl-methyl-phenylphosphaniumyl)boranuide；(hydroxymethyl-methyl-phenylphosphaniumyl)boranuide
• CAS: 281667-51-4
• 化学式: C₈H₁₄BOP
• 分子量: 167.983
• InChiKey: QKBAYOUVPBRCEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.19
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-hydroxymethyl(methyl)phenylphosphine-borane 在 ruthenium trichloride 、 氢氧化钾 、 dipotassium peroxodisulfate 作用下， 以 水 、 乙腈 为溶剂， 生成 (R)-(+)-[(O-methyl)methylphenylphosphinite]borane
  参考文献：
  名称：

  烷基（二甲基）膦-硼烷的立体选择性氧化一碳降解。对映体富集的仲膦硼烷的合成

  摘要：

  DOI：

  10.1021/jo9918201
• 作为产物：
  描述：

  dimethylphenylphosphine borane 在 仲丁基锂 、 氧气 、 鹰爪豆碱 、 亚磷酸三乙酯 作用下， 以 乙醚 、 环己烷 为溶剂， 反应 1.0h， 以69%的产率得到(R)-hydroxymethyl(methyl)phenylphosphine-borane
  参考文献：
  名称：

  烷基（二甲基）膦-硼烷的立体选择性氧化一碳降解。对映体富集的仲膦硼烷的合成

  摘要：

  DOI：

  10.1021/jo9918201

文献信息

• Parallel and Modular Synthesis of P-Chirogenic <i>P,O</i>-Ligands
  作者：Magnus J. Johansson、Susanne Berglund、Yinjun Hu、Kristian H. O. Andersson、Nina Kann

  DOI：10.1021/co2002119

  日期：2012.5.14

  A modular synthesis of P-chirogenic α-alkoxyphosphine ligands has been developed, allowing for the variation of two of the three groups on phosphorus. Oxidation and concomitant desymmetrization of a prochiral alkyl- or aryldimethylphosphine borane afforded α-hydroxyphosphines, which were subsequently deprotonated and alkylated in a parallel fashion. The choice of base and temperature for the alkylation

  已经开发了P-手性α-烷氧基膦配体的模块合成，其允许磷上的三个基团中的两个发生变化。前手性烷基或芳基二甲基膦硼烷的氧化和伴随的脱对称化得到α-羟基膦，其随后以平行方式被去质子化和烷基化。发现烷基化步骤的碱和温度的选择对于反应的结果至关重要。随后在钯催化的烯丙基取代中筛选选择的配体，以良好至优异的产率提供产物，但对映选择性适中，这表明需要进一步优化配体结构以增加立体选择性。
• P-Chirogenic Phosphine/Sulfide Hybrid Ligands
  作者：Hiroshi Sugama、Hirohisa Saito、Hiroshi Danjo、Tsuneo Imamoto

  DOI：10.1055/s-2001-18433

  日期：——

  P-Chirogenic phosphine/sulfide hybrid ligands 1 were prepared by the use of optically active phosphine-boranes as the intermediates. The palladium complexes of the ligands exhibited high catalytic activity and enantioselectivity in allylic alkylation of 1-acetoxy-1,3-diphenylprop-2-ene with malonate esters.

  P-手性磷/硫杂合配体1是通过光学活性磷-硼烷作为中间体制备的。这些配体的钯复合物在与马来酸酯的1-乙酸氧基-1,3-二苯基丙-2-烯的烯基烷基化反应中表现出高催化活性和优良的对映选择性。
• 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.
• H-Adamantylphosphinates as Universal Precursors of P-Stereogenic Compounds
  作者：David Gatineau、Duc Hanh Nguyen、Damien Hérault、Nicolas Vanthuyne、Julien Leclaire、Laurent Giordano、Gérard Buono

  DOI：10.1021/acs.joc.5b00548

  日期：2015.4.17

  A new family of H-adamantylphosphinates as universal precursors of P-stereogenic ligands was obtained in one step from commercial chlorophosphines. Both enantiomers of these air- and moisture-stable intermediates can easily be separated by semipreparative chiral HPLC on a gram scale and individually undergo stereoselective transformations to afford each enantiomer of a set of P-stereogenic compounds such as secondary phosphine oxides and boron-protected monophosphines.