(R)-biphenylphenylphosphine 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)-biphenylphenylphosphine oxide
• 英文别名: (S)-biphenylphenylphosphine oxide；(S)-(2-phenylphenyl)phenylphosphine oxide
• 化学式: C₁₈H₁₅OP
• 分子量: 278.3
• InChiKey: ZNQGQBOMTUUJAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl phenylphosphinate 、 biphenyl-2-yl-lithium 以 四氢呋喃 为溶剂， 以98%的产率得到(R)-biphenylphenylphosphine oxide
  参考文献：
  名称：

  Enantioselective synthesis of secondary phosphine oxides from (RP)-(−)-menthyl hydrogenophenylphosphinate

  摘要：

  Alkyl- and arylphenylphosphine oxides can easily be synthesized with an excellent enantiomeric excess starting from diastereomerically pure (Rp)-(-)-menthylhydrogenophenylphosphinate and organometallic reagents. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.05.140

文献信息

• Palladium-Catalyzed Synthesis of Dibenzophosphole Oxides via Intramolecular Dehydrogenative Cyclization
  作者：Yoichiro Kuninobu、Takuya Yoshida、Kazuhiko Takai

  DOI：10.1021/jo201030j

  日期：2011.9.16

  Dibenzophosphole oxides were obtained from secondary hydrophosphine oxides with a biphenyl group by dehydrogenation via phosphine–hydrogen and carbon–hydrogen bond cleavage in the presence of a catalytic amount of palladium(II) acetate, Pd(OAc)2. By using this reaction, a ladder-type dibenzophosphole oxide could also be synthesized by double intramolecular dehydrogenative cyclization.

  在催化量的乙酸钯（II）Pd（OAc）2存在下，通过膦-氢和碳-氢键的裂解，从具有联苯基的仲氢氧化膦中获得二苯并磷氧化物。通过使用该反应，也可以通过分子内双脱氢环化来合成梯型二苯甲酰氧化物。
• Synthesis of P-stereogenic secondary phosphine oxides using α-d-glucosamine as a chiral precursor
  作者：Laurent Copey、Ludivine Jean-Gérard、Bruno Andrioletti、Eric Framery

  DOI：10.1016/j.tetlet.2015.12.074

  日期：2016.2

  Secondary phosphine oxides were synthesized using a two-step procedure: a basic hydrolysis of oxazaphospholidine SP-2 to form the secondary phosphinate RP-4, followed by the stereoselective nucleophilic attack of organometallic reagents to obtain the expected enantioenriched secondary phosphine oxides.

  次级膦氧化物的合成过程分两步进行：将氧杂氮磷吡啶S P -2进行碱性水解以形成次级次膦酸酯R P -4，然后对有机金属试剂进行立体选择性亲核攻击，从而获得预期的对映体富集的次级膦氧化物。
• Enantioseparation of<i>P</i>-Stereogenic Secondary Phosphine Oxides and Their Stereospecific Transformation to Various Tertiary Phosphine Oxides and a Thiophosphinate
  作者：Bence Varga、Péter Szemesi、Petra Nagy、Réka Herbay、Tamás Holczbauer、Elemér Fogassy、György Keglevich、Péter Bagi

  DOI：10.1021/acs.joc.1c01364

  日期：2021.11.5

  Secondary phosphine oxides incorporating various aryl and alkyl groups were synthesized in racemic form, and these products formed the library reported in this study. TADDOL derivatives were used to obtain the optical resolution of these P-stereogenic secondary phosphine oxides. The developed resolution method showed a good scope under the optimized reaction conditions, as 9 out of 14 derivatives could

  包含各种芳基和烷基的二级氧化膦以外消旋形式合成，这些产物形成了本研究报告的库。TADDOL 衍生物用于获得这些P-立体二氧化膦的光学拆分。所开发的拆分方法在优化的反应条件下显示出良好的范围，因为 14 种衍生物中有 9 种可以用对映体过量 (ee) ≥ 79% 制备，并且这些衍生物中有 5 种实​​际上是对映体纯的 >P(O)H 化合物 (ee ≥ 98%）。还证明了这种解析方法的可扩展性。通过单晶 XRD 测量阐明了导致非对映复合物形成的非共价相互作用。(秒)-(2-甲基苯基)苯基氧化膦在立体定向的 Michaelis-Becker、Hirao 或 Pudovik 反应中被转化为各种P-立体叔氧化膦和硫代次膦酸盐。
• Manganese-Catalyzed and Mediated Synthesis of Arylphosphinates and Related Compounds
  作者：Olivier Berger、Jean-Luc Montchamp

  DOI：10.1021/acs.joc.9b01239

  日期：2019.7.19

  H-phosphinates and related compounds was examined. A practical catalytic process with the air as the oxidant could not be found. However, an inexpensive and robust methodology was developed, using catalytic Mn(II) as the radical initiator and excess Mn(IV) as the stoichiometric oxidant. Using these conditions, the inter- and intramolecular arylation of phosphinylidene compounds has a broad scope, including

  检查了H-次膦酸酯和相关化合物的自由基芳基化。找不到以空气为氧化剂的实际催化方法。但是，开发了一种廉价而稳健的方法，使用了催化性的Mn（II）作为自由基引发剂，而过量的Mn（IV）作为化学计量的氧化剂。使用这些条件，次膦基化合物的分子间和分子内芳基化具有广泛的范围，包括应用于合成P-杂环。完整介绍了该方法，并讨论了其局限性。
• Stereoselective Addition of Grignard Reagents to New P-Chirogenic N-Phosphinoylbenzaldimines: Effect of the Phosphorus Substituents on the Stereoselectivity
  作者：Irene Notar Francesco、Coraline Egloff、Alain Wagner、Françoise Colobert

  DOI：10.1002/ejoc.201100380

  日期：2011.7

  give both diastereoisomers in high yields and with promising diastereomeric ratios. Then N-[(tert-butyl)(phenyl)phosphinoyl]benzaldimine, which displayed the best results, was subjected to the 1,2-addition of various Grignard reagents to evaluate the best chiral induction due to the stereogenic phosphorus atom. The corresponding adducts were obtained in excellent yields and with moderate to excellent diastereoisomeric

  通过从合适的氧化膦开始，通过五个步骤合成了几种膦亚胺，然后用甲基溴化镁处理，以高产率和有希望的非对映异构体比例得到两种非对映异构体。然后将显示出最佳结果的 N-[(叔丁基)(苯基)膦酰基]苯扎二亚胺进行各种格氏试剂的 1,2-加成，以评估由于立体磷原子引起的最佳手性诱导。以极好的收率和中等至极好的非对映异构体比率获得了相应的加合物。