(S_ax)-2,2'-bis(diphenylphosphinopyl)-3,3',6,6'-tetrakis(methoxy)-1,1'-biphenyl

• 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: (S_ax)-2,2'-bis(diphenylphosphinopyl)-3,3',6,6'-tetrakis(methoxy)-1,1'-biphenyl
• 英文别名: 2-diphenylphosphoryl-3-(2-diphenylphosphoryl-3,6-dimethoxyphenyl)-1,4-dimethoxybenzene
• 化学式: C₄₀H₃₆O₆P₂
• 分子量: 674.67
• InChiKey: DUAVIQZUMOCONL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  48
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S_ax)-2,2'-bis(diphenylphosphinopyl)-3,3',6,6'-tetrakis(methoxy)-1,1'-biphenyl 在 三氯硅烷 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以90%的产率得到[2-(2-diphenylphosphanyl-3,6-dimethoxyphenyl)-3,6-dimethoxyphenyl]-diphenylphosphane
  参考文献：
  名称：

  锰（III）介导的芳烃直接膦酰化

  摘要：

  锰（III）促进的单-和二取代的芳烃与亚磷酸二烷基酯的直接膦酰化反应可以很好地提供区域选择性的二烷基膦酸酯。该反应可适用于带有给电子基团和吸电子基团如酯和腈的芳烃。

  DOI：

  10.1016/j.tetlet.2010.03.029
• 作为产物：
  描述：

  (R,R)-phthalic acid bis{1-[3-(diphenyl-phosphinoyl)-2-iodo-4-methoxy-phenoxycarbonyl]-2,2-dimethylpropyl} ester 在 氢氧化钾 、 铜 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 生成 (S_ax)-2,2'-bis(diphenylphosphinopyl)-3,3',6,6'-tetrakis(methoxy)-1,1'-biphenyl
  参考文献：
  名称：

  非对映体分子内乌尔曼偶联：独特的手性助剂，用于制备3,3'-二取代的MeO-BIPHEP衍生物。

  摘要：

  [反应：见正文]描述了一种手性助剂，在分子内Ullmann偶联过程中仅提供一种非对映异构体。在115摄氏度的DMF中用铜粉处理五种Ullmann偶联前体，得到2,2'，3,3'，6,6'-六取代的1,1'-联苯作为单一非对映异构体，收率范围为66％至91％ 。

  DOI：

  10.1021/ol060484p

文献信息

• Use of ¹H NMR chemical shifts to determine the absolute configuration and enantiomeric purity for enantiomers of 3,3′-disubstituted-MeO-BIPHEP derivatives
  作者：Evgueni Gorobets、Masood Parvez、Bronwen MM Wheatley、Brian A Keay

  DOI：10.1139/v05-230

  日期：2006.2.1

  The absolute configuration of a series of 3,3′-disubstituted-MeO-BIPHEP derivatives can be determined by the 1H NMR chemical shift of the methoxyl group when the 3,3′-disubsituted-MeO-BIPHEP deriva...

  一系列3,3'-二取代-MeO-BIPHEP衍生物的绝对构型可以通过3,3'-二取代-MeO-BIPHEP衍生物时甲氧基的1H NMR化学位移确定。
• Selective ortho lithiation of (2,5-dimethoxyphenyl)diphenylphosphine oxide and trapping of the resulting aryllithium with electrophiles
  作者：John M. Brown、Simon Woodward

  DOI：10.1021/jo00024a019

  日期：1991.11

  The title compound undergoes predominant 6-lithiation, ortho to the methoxy and phosphinoyl groups, on reaction with t-BuLi in THF under conditions of thermodynamic control at low temperature. The organolithium compound is stable at least to 0-degree-C and can be trapped by a range of electrophiles to give the corresponding tetrasubstituted (diphenylphosphinoyl)arenes in moderate to good yield. The iodide formed by this sequence undergoes Ullman coupling to the diphenyl, which exhibits a novel restricted rotation phenomenon, in good yield under mild conditions. (2,5-Dimethoxyphenyl)diphenylphosphine sulfide lithiates exclusively at the 4-position under the same conditions, whilst the corresponding phosphine is unreactive.
• Synthesis, resolution and applications of 3,3′-bis(RO)-MeO-BIPHEP derivatives
  作者：Evgueni Gorobets、Guang-Ri Sun、Bronwen M.M. Wheatley、Masood Parvez、Brian A. Keay

  DOI：10.1016/j.tetlet.2004.03.073

  日期：2004.4

  A series of optically pure 3,3'-bis(RO)-MeO-BIPHEP derivatives are prepared and used in palladium catalyzed asymmetric transformations. The phosphine oxide of (+/-)-5 is prepared in four steps from p-methoxyphenol and resolved using the novel resolving reagent chloro((L)-menthoxy)dimethylsilane. Subsequent conversions provide catalysts 8 and 9. Ligands 6, 7 and 10 are prepared in six steps from p-methoxyphenol and the phosphine oxides of 6 and 7, and 10 are resolved using di-p-toluoyl- and dibenzoyl-(L)-tartaric acid, respectively. (R)-3,3'-Bispivalate 8 is superior to the other catalysts in asymmetric Heck reaction with 2,3-dihydrofuran while (R)-(+)-bis(tolyloxy) 10 and (+)-(R)-sugar derivative 9 are better in the Pd-catalyzed polyene cyclization; however, the absolute sense of chirality in the product from the polyene cyclization was reversed to that obtained when (R)-(+)BINAP and (R)-(+)-MeO-BIPHEP were used. (C) 2004 Elsevier Ltd. All rights reserved.
• Manganese(III)-mediated direct phosphonylation of arenes
  作者：Wei Xu、Jian-Ping Zou、Wei Zhang

  DOI：10.1016/j.tetlet.2010.03.029

  日期：2010.5

  Manganese (III)-promoted direct phosphonylation of mono- and disubstituted arenes with dialkylphosphite afforded regioselective dialkylphosphonates in good yields. The reactions can apply to arenes bearing electron-donating groups and electron-withdrawing groups such as ester and nitrile.

  锰（III）促进的单-和二取代的芳烃与亚磷酸二烷基酯的直接膦酰化反应可以很好地提供区域选择性的二烷基膦酸酯。该反应可适用于带有给电子基团和吸电子基团如酯和腈的芳烃。
• Diastereospecific Intramolecular Ullmann Couplings:  Unique Chiral Auxiliary for the Preparation of 3,3‘-Disubstituted MeO-BIPHEP Derivatives
  作者：E. Gorobets、R. McDonald、B. A. Keay

  DOI：10.1021/ol060484p

  日期：2006.3.1

  auxiliary is described that provides only one diastereomer during intramolecular Ullmann couplings. Treatment of five Ullmann coupling precursors with Cu powder in DMF at 115 degrees C provides 2,2',3,3',6,6'-hexasubstituted 1,1'-biphenyls as single diastereomers in yields ranging from 66% to 91%.

  [反应：见正文]描述了一种手性助剂，在分子内Ullmann偶联过程中仅提供一种非对映异构体。在115摄氏度的DMF中用铜粉处理五种Ullmann偶联前体，得到2,2'，3,3'，6,6'-六取代的1,1'-联苯作为单一非对映异构体，收率范围为66％至91％ 。