bis(3,5-dimethylphenyl)phosphinooxygen | 866324-40-5

• 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(3,5-dimethylphenyl)phosphinooxygen
• 英文别名: bis(3,5-dimethylphenyl)oxyphosphine；di(3,5-dimethylphenyl)oxyphosphine；Phosphinous acid, bis(3,5-dimethylphenyl)-；bis(3,5-dimethylphenyl)phosphinous acid
• CAS: 866324-40-5
• 化学式: C₁₆H₁₉OP
• 分子量: 258.3
• InChiKey: KPVSNHKBKLAELF-UHFFFAOYSA-N

物化性质

• 沸点：
  424.6±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  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：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(3,5-dimethylphenyl)phosphinooxygen 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以64%的产率得到双(3,5-二甲苯基)磷
  参考文献：
  名称：

  Synthesis of achiral, but unsymmetric, seven-membered rhodium(I)-chelates for hydrogenation in the chiral environment of alkyl polyglucoside micelles

  摘要：

  Chiral rhodium(I) chelates containing a seven-membered ring are well-known active catalysts for the asymmetric hydrogenation of amino acid precursors. A high conformational flexibility allows their enantioselectivity to be strongly influenced by modifiers. Now we show the nature of the counter-ions to have a large influence in apolar solvents. In addition, the presence of micelle forming alkyl polyglycosides as amphiphiles causes a remarkable increase in the enantiomeric excess (%ee). However, on achiral catalysts this enantioselectivity inducing effect scarcely exceeds the standard deviation for the gas chromatographic determination of the enantiomeric ratio. This is also true for the application of unsymmetric P,P'-ligands such as 3-phosphinopropyl-phosphinites or butane-1,4-diyl-bis(phosphines) carrying different P'-aryl groups, for which synthetic routes are given. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00845-7
• 作为产物：
  描述：

  3,5-二甲基溴苯 在 magnesium 、 二乙基亚磷酸氢酯 作用下， 以 乙醚 为溶剂， 生成 bis(3,5-dimethylphenyl)phosphinooxygen
  参考文献：
  名称：

  Synthesis of achiral, but unsymmetric, seven-membered rhodium(I)-chelates for hydrogenation in the chiral environment of alkyl polyglucoside micelles

  摘要：

  Chiral rhodium(I) chelates containing a seven-membered ring are well-known active catalysts for the asymmetric hydrogenation of amino acid precursors. A high conformational flexibility allows their enantioselectivity to be strongly influenced by modifiers. Now we show the nature of the counter-ions to have a large influence in apolar solvents. In addition, the presence of micelle forming alkyl polyglycosides as amphiphiles causes a remarkable increase in the enantiomeric excess (%ee). However, on achiral catalysts this enantioselectivity inducing effect scarcely exceeds the standard deviation for the gas chromatographic determination of the enantiomeric ratio. This is also true for the application of unsymmetric P,P'-ligands such as 3-phosphinopropyl-phosphinites or butane-1,4-diyl-bis(phosphines) carrying different P'-aryl groups, for which synthetic routes are given. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00845-7

文献信息

• Novel olefination process to itaconate and succinate derivatives
  申请人：——

  公开号：US20020058832A1

  公开（公告）日：2002-05-16

  An efficient and selective process, capable of scale-up, to make itaconate derivatives of formula (IV), and/or succinate derivatives of formula (V) and/or (VI) by asymmetric hydrogenation of the itaconate derivatives. 1

  一种高效且选择性的工艺，可扩大规模，通过对顺丁烯二酸衍生物进行不对称加氢，制备化学式（IV）的顺丁烯二酸衍生物，以及/或化学式（V）和/或（VI）的琥珀酸衍生物。
• Chiral Bifunctional Phosphine-Carboxylate Ligands for Palladium(0)-Catalyzed Enantioselective C−H Arylation
  作者：Lei Yang、Markus Neuburger、Olivier Baudoin

  DOI：10.1002/anie.201712061

  日期：2018.1.26

  Previous enantioselective Pd0‐catalyzed C−H activation reactions proceeding via the concerted metalation‐deprotonation mechanism employed either a chiral ancillary ligand, a chiral base, or a bimolecular mixture thereof. This study describes the development of new chiral bifunctional ligands based on a binaphthyl scaffold which incorporates both a phosphine and a carboxylic acid moiety. The optimal

  先前的对映选择性Pd 0催化的CH活化反应是通过手性辅助配体，手性碱或它们的双分子混合物通过一致的金属化-去质子化机理进行的。这项研究描述了基于双萘基支架的新手性双功能配体的开发，该萘并膦既包含膦又包含羧酸部分。最佳配体为解对称的C（sp 2）-H芳基化反应提供了高收率和对映选择性，从而导致5,6-二氢菲啶，而相应的单官能配体显示出低对映选择性。事实证明，该双功能体系适用于一系列取代的二氢菲啶，并允许消旋底物的平行动力学拆分。
• SYNTHESIS AND USE OF OXA-SPIRODIPHOSPHINE LIGAND
  申请人：SHENZHEN CATALYS SCIENCE AND TECHNOLOGY CO., LTD.

  公开号：US20200308206A1

  公开（公告）日：2020-10-01

  The present invention relates to the technical field of chiral synthesis, and specifically provides a new type of oxa-spirodiphosphine ligands. The bisphosphine ligand is prepared with oxa-spirobisphenol as a starting material after triflation, palladium catalyzed coupling with diaryl phosphine oxide, reduction of trichlorosilane, further palladium catalyzed coupling with diaryl phosphine oxide, and further reduction of trichlorosilane. The oxa-spiro compound has central chirality, and thus includes L-oxa-spirodiphosphine ligand and R-oxa-spirodiphosphine ligand. The racemic spirodiphosphine ligand is capable of being synthesized from racemic oxa-spirobisphenol as a raw material. The present invention can be used as a chiral ligand in the asymmetric hydrogenation of unsaturated carboxylic adds. The complex of the ligand with ruthenium can achieve an enantioselectivity of greater than 99% in the asymmetric hydrogenation of methyl-cinnamic acid.

  本发明涉及手性合成技术领域，具体提供了一种新型的氧杂环螺环二膦配体。该双膦配体是通过氧杂环螺双苯酚作为起始材料，经过三氟甲磺酰化、钯催化偶联二芳基氧膦、三氯硅烷还原、进一步的钯催化偶联二芳基氧膦和进一步的三氯硅烷还原制备而成。氧杂环螺化合物具有中心手性，因此包括L-氧杂环螺环二膦配体和R-氧杂环螺环二膦配体。外消旋螺环二膦配体可从外消旋氧杂环螺双苯酚作为原料合成。本发明可用作不饱和羧酸不对称氢化的手性配体。该配体与钌的配合物在对甲基肉桂酸的不对称氢化中可实现大于99%的对映选择性。
• 氧杂螺环双膦配体的合成与应用
  申请人：凯特立斯（深圳）科技有限公司

  公开号：CN110128471B

  公开（公告）日：2021-01-15

  本发明专利属于手性合成技术领域，具体提供了一类新型氧杂螺环双膦配体的合成与应用。该双膦配体从氧杂螺环二酚出发经过三氟甲磺酰化、钯催化二芳基氧膦偶联、三氯硅氢还原、再次钯催化二芳基氧膦偶联和再次的三氯硅氢还原制备得到。该氧杂螺环化合物具有中心手性，因此有左旋氧杂螺环双膦配体和右旋氧杂螺环双膦配体，消旋的螺环双膦配体可以通过消旋的氧杂螺环二酚为原料合成得到。本发明可以作为手性配体用于不饱和羧酸的不对称氢化中。其与钌的络合物在甲基‑肉桂酸的不对称氢化中可以得到大于99％的对映选择性。
• N-Functionalization of β-aminophosphonates: cytotoxic effects of the new derivatives
  作者：György Keglevich、Petra Regina Varga、Emőke Dinnyési、Zsuzsanna Szalai、Szilvia Bősze、Oláhné Szabó Rita、László Drahos、Konstantin Karaghiosoff

  DOI：10.1039/d4ob00243a

  日期：——

  β-Aminophosphonates obtained by the Michael addition of primary amines to the double bond of diethyl vinylphosphonate proved to be suitable starting materials (amine components) in the Kabachnik–Fields reaction with formaldehyde and dialkyl phosphites or secondary phosphine oxides to afford N-phosphonylmethyl- and N-phosphinoylmethyl-β-aminophosphonates. On the other hand, the starting aminophosphonates

  通过将伯胺迈克尔加成到乙烯基膦酸二乙酯的双键上而获得的β-氨基膦酸酯被证明是与甲醛和亚磷酸二烷基酯或仲膦氧化物进行Kabachnik-Fields反应的合适起始原料（胺组分），得到N-膦酰基甲基-和N-膦酰基甲基-β-氨基膦酸酯。另一方面，起始氨基膦酸酯通过使用酰基氯的N-酰化进行修饰。如宽 NMR 信号所示，发现N-酰基产物存在于两种构象异构体的动态平衡中。在 26 °C 时，可能会围绕酰胺官能团的 N-C 轴发生旋转。同时，-5 °C 的低温 NMR 测量揭示了两种不同旋转异构体的存在，可以通过31 P、 13 C 和1 H NMR 数据来表征。修饰的β-氨基膦酸衍生物对MDA-MB-231、PC-3、A431和Ebc-1肿瘤细胞系进行了比较结构活性分析，在少数情况下检测到了显着的活性。