bis(3-fluoro-5-methylphenyl)phosphine oxide | 748189-29-9

• 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: bis(3-fluoro-5-methylphenyl)phosphine oxide
• 英文别名: 1-Fluoro-3-(3-fluoro-5-methylphenyl)phosphonoyl-5-methylbenzene；1-fluoro-3-(3-fluoro-5-methylphenyl)phosphonoyl-5-methylbenzene
• CAS: 748189-29-9
• 化学式: C₁₄H₁₃F₂OP
• 分子量: 266.227
• InChiKey: BSBRLAANKARFAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(3-fluoro-5-methylphenyl)phosphine oxide 在 三氯化磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  Electronic Control of Chiral Quaternary Center Creation in the Intramolecular Asymmetric Heck Reaction

  摘要：

  The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.

  DOI：

  10.1021/jo049448z
• 作为产物：
  描述：

  3-溴-5-氟甲苯 在 对丁基溴苯 、 碘 、 magnesium 、 亚磷酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成 bis(3-fluoro-5-methylphenyl)phosphine oxide
  参考文献：
  名称：

  醌亚胺缩酮与Ar 2 P（O）H的高度化学和区域选择性C–P交叉偶联反应，构建邻氨基三芳基膦衍生物

  摘要：

  通过涉及醌亚胺缩酮（QIK）与Ar 2 P（O）H的C-P交叉偶联反应，并通过Lewis碱催化，已经获得了一种高度化学和区域选择性的方法来构建邻氨基三芳基膦氧化物。该替代方案提供了广泛的底物范围，具有优异的收率（82–95％），并且通过进一步的还原反应以高收率（87–95％）获得了多种邻氨基三芳基膦。此外，该反应可以扩大规模，并完成了一些合成转化，以构建功能化的有机磷。

  DOI：

  10.1039/c9gc00989b

文献信息

• A Superior Method for the Reduction of Secondary Phosphine Oxides
  作者：Carl A. Busacca、Jon C. Lorenz、Nelu Grinberg、Nizar Haddad、Matt Hrapchak、Bachir Latli、Heewon Lee、Paul Sabila、Anjan Saha、Max Sarvestani、Sherry Shen、Richard Varsolona、Xudong Wei、Chris H. Senanayake

  DOI：10.1021/ol0517832

  日期：2005.9.1

  to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70

  [反应：见正文]已发现氢化二异丁基铝（DIBAL-H）和三异丁基铝是仲氧化膦（SPO）的杰出还原剂。所有类别的SPO都可以轻松还原，包括二芳基，芳基烷基和二烷基成员。现在可以在低温下还原许多SPO，并发现了保存可还原官能团的条件。即使是最富电子和位阻的膦氧化物，也可以在50-70摄氏度的温度下在几小时内还原。这种新的还原方法与现有技术相比具有明显的优势。
• Highly chemo- and regioselective C–P cross-coupling reaction of quinone imine ketals with Ar₂P(O)H to construct <i>ortho</i>-amino triarylphosphine derivatives
  作者：Teng Liu、Yongqin Li、Feixiang Cheng、Xianfu Shen、Jianjun Liu、Jun Lin

  DOI：10.1039/c9gc00989b

  日期：——

  A highly chemo- and regioselective approach for the construction of ortho-amino triarylphosphine oxides has been achieved through a C–P cross-coupling reaction involving quinone imine ketals (QIKs) with Ar2P(O)H and catalyzed via a Lewis base. This alternative protocol provided a wide substrate scope with excellent yields (82–95%), and a variety of ortho-amino triarylphosphines were obtained with high

  通过涉及醌亚胺缩酮（QIK）与Ar 2 P（O）H的C-P交叉偶联反应，并通过Lewis碱催化，已经获得了一种高度化学和区域选择性的方法来构建邻氨基三芳基膦氧化物。该替代方案提供了广泛的底物范围，具有优异的收率（82–95％），并且通过进一步的还原反应以高收率（87–95％）获得了多种邻氨基三芳基膦。此外，该反应可以扩大规模，并完成了一些合成转化，以构建功能化的有机磷。
• SYNTHESIS OF ELECTRON-DEFICIENT SECONDARY PHOSPHINE OXIDES AND SECONDARY PHOSPHINES: BIS[3,5-BIS(TRIFLUOROMETHYL)PHENYL]PHOSPHINE OXIDE and BIS[3,5-BIS(TRIFLUOROMETHYL)PHENYL]PHOSPHINE
  作者：Busacca, Carl A.、Lorenz, Jon C.、Sabila, Paul、Haddad, Nizar、Senandyake, Chris H.、Denmark, Scott E.、Regens, Christopher S.

  DOI：10.15227/orgsyn.084.0242

  日期：——
• An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
  作者：Teng Liu、Yanqiong Zhang、Rong Yu、Jianjun Liu、Feixiang Cheng

  DOI：10.1055/s-0039-1690709

  日期：2020.1

  An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.

  一种无金属、高效且实用的方法用于制备磷硫酸酯，通过在大气氧气存在下，以四丁基碘化铵（TBAI）为催化剂，利用磺酰肼与二级膦氧化物进行氧化交叉脱氢偶联（CDC）反应建立。该策略以良好至优异的产率提供多样的磷硫酸酯。此外，利用该方法，还可以在克级规模上合成两种代表性的生物活性分子。
• Electronic Control of Chiral Quaternary Center Creation in the Intramolecular Asymmetric Heck Reaction
  作者：Carl A. Busacca、Danja Grossbach、Scot J. Campbell、Yong Dong、Magnus C. Eriksson、Robert E. Harris、Paul-James Jones、Ji-Young Kim、Jon C. Lorenz、Keith B. McKellop、Erin M. O'Brien、Fenghe Qiu、Robert D. Simpson、Lana Smith、Regina C. So、Earl M. Spinelli、Jana Vitous、Chiara Zavattaro

  DOI：10.1021/jo049448z

  日期：2004.8.1

  The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.