(1-(pyridin-2-yl)ethane-1,2-diyl)bis(diphenylphosphine 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: (1-(pyridin-2-yl)ethane-1,2-diyl)bis(diphenylphosphine oxide)
• 英文别名: 2-[1,2-Bis(diphenylphosphoryl)ethyl]pyridine；2-[1,2-bis(diphenylphosphoryl)ethyl]pyridine
• 化学式: C₃₁H₂₇NO₂P₂
• 分子量: 507.508
• InChiKey: ABTSNFOXEGGXHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  47
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(1,2-bis(diphenylphosphanyl)ethyl)pyridine 在 双氧水 作用下， 反应 1.0h， 生成 (1-(pyridin-2-yl)ethane-1,2-diyl)bis(diphenylphosphine oxide)
  参考文献：
  名称：

  在炔烃上依次向膦中添加膦，以在催化下选择性合成1,2-二膦基乙烷。定义明确的NHC铜磷酸盐与原位CuCl2 / NHC催化剂

  摘要：

  The well-defined NHC-copper phosphides [(NHC)CuPPh2](3) (1, NHC = 1,3-diisopropy1-4,5-dimethyli- midazol-2-ylidene (I'Pr); 2, NHC = N,N-di-tert-butylimidazol-2-ylidene ((IBu)-Bu-t)) have been prepared by the reaction of simple copper halides with HPPh2 in the presence of N-heterocyclic carbenes (NHCs). Complexes 1 and 2 enabled catalytic double hydrophosphination of alkyl and aryl terminal alkynes to yield 1,2-diphosphinoethanes selectively in good yields. On the basis of these results, the most efficient and pratical in situ CuCl2/NHC catalyst has been developed. It catalyzes the selective double hydrophosphination of the alkynes with high efficiency and a wide substrate scope and exhibits even better performance than the well-defined NHC-Cu phosphides. The mechanistic studies disclosed that the formation of a copper acetylide in the catalytic cycle played an important role in the acceleration of the catalytic process.

  DOI：

  10.1021/acs.organomet.6b00854

文献信息

• Alkali Metal Catalysed Double Hydrophosphorylation of Nitriles and Alkynes
  作者：Indrani Banerjee、Adimulam Harinath、Tarun K. Panda

  DOI：10.1002/ejic.201900164

  日期：2019.4.30

  The potassium congener was observed to be the most efficient catalyst for converting aryl nitriles to the corresponding N-((diphenyl-phosphoryl)(aryl)methyl)-P,P-diphenylphosphinic amide [ArCHP(O)-Ph 2 NHP(O)Ph 2 ] at mild temperature (60 °C) and with neat reactants. Double hydrophosphorylation of alkynes with HP(O)Ph 2 is also very effective when [KN(SiMe 3 ) 2 ] is used as a precatalyst at room temperature

  据报道，使用碱金属预催化剂 [MN(SiMe 3 ) 2 ] (M = Li, Na, K)，通过腈与二苯基膦氧化物的双氢磷酸化催化 C-P 和 N-P 键的形成。据观察，钾同系物是将芳基腈转化为相应的 N-((二苯基磷酰基)(芳基)甲基)-P,P-二苯基次膦酰胺 [ArCHP(O)-Ph 2 NHP(O) Ph 2 ] 在温和的温度 (60 °C) 下和纯反应物。当 [KN(SiMe 3 ) 2 ] 在室温下用作预催化剂时，炔烃与 HP(O)Ph 2 的双氢磷酸化也非常有效，并得到相应的 1,2-二基双（二苯基膦氧化物 [RCHP(O) )Ph 2 CH 2 P(O)Ph 2 ] 作为产物。探索了两种反应的更广泛的底物范围。
• An efficient base-catalyzed double addition of H-phosphine oxides to alkynes
  作者：Aya Yoshimura、Yuta Saga、Yuki Sato、Akiya Ogawa、Tieqiao Chen、Li-Biao Han

  DOI：10.1016/j.tetlet.2016.06.079

  日期：2016.7

  An efficient base-catalyzed double addition of H-phosphine oxides to alkynes is developed. In the presence of a catalytic amount of a base, the addition of various H-phosphine oxides to both aromatic and aliphatic alkynes took place efficiently to produce the corresponding bisphosphoryl compounds in excellent yields. This method provides an easy direct way to prepare bisphosphine oxides that are of

  开发了一种高效的碱催化的H-膦氧化物双加成炔烃。在催化量的碱的存在下，向芳族和脂族炔烃中都有效地添加了各种H-膦氧化物，从而以优异的产率生产了相应的双磷酰基化合物。该方法提供了一种简单直接的方法来制备在有机合成中非常重要的双膦氧化物。
• Air-induced double addition of P(O)–H bonds to alkynes: a clean and practical method for the preparation of 1,2-bisphosphorylethanes
  作者：Haiqing Guo、Aya Yoshimura、Tieqiao Chen、Yuta Saga、Li-Biao Han

  DOI：10.1039/c6gc03240k

  日期：——

  An air-induced double addition of diphenyl phosphine oxide to various alkynes was reported. This reaction can proceed efficeintly under metal- and solvent-free conditions, and is a clean and practically useful...

  据报道，在空气中向各种炔烃中双重添加了二苯基氧化膦。该反应可以在无金属和无溶剂的条件下有效地进行，并且是干净且实用的...
• Facile synthesis of chelating bisphosphine oxides and bisphosphines via palladium-catalyzed bishydrophosphinylation reactions
  作者：Aberdeen Allen、Ling Ma、Wenbin Lin

  DOI：10.1016/s0040-4039(02)00609-3

  日期：2002.5

  A series of functional bisphosphosphine oxides were synthesized in good yields via new Pd-catalyzed bis-hydrophosphinylation reactions of terminal alkynes and diphenylphosphine oxide. The resulting bisphosphine oxides were reduced to their corresponding bisphosphines in quantitative yields via a Ti((OPr)-Pr-i)(4)-mediated process. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Sequential Addition of Phosphine to Alkynes for the Selective Synthesis of 1,2-Diphosphinoethanes under Catalysis. Well-Defined NHC-Copper Phosphides vs in Situ CuCl₂/NHC Catalyst
  作者：Jia Yuan、Lizhao Zhu、Jianying Zhang、Jianfeng Li、Chunming Cui

  DOI：10.1021/acs.organomet.6b00854

  日期：2017.1.23

  The well-defined NHC-copper phosphides [(NHC)CuPPh2](3) (1, NHC = 1,3-diisopropy1-4,5-dimethyli- midazol-2-ylidene (I'Pr); 2, NHC = N,N-di-tert-butylimidazol-2-ylidene ((IBu)-Bu-t)) have been prepared by the reaction of simple copper halides with HPPh2 in the presence of N-heterocyclic carbenes (NHCs). Complexes 1 and 2 enabled catalytic double hydrophosphination of alkyl and aryl terminal alkynes to yield 1,2-diphosphinoethanes selectively in good yields. On the basis of these results, the most efficient and pratical in situ CuCl2/NHC catalyst has been developed. It catalyzes the selective double hydrophosphination of the alkynes with high efficiency and a wide substrate scope and exhibits even better performance than the well-defined NHC-Cu phosphides. The mechanistic studies disclosed that the formation of a copper acetylide in the catalytic cycle played an important role in the acceleration of the catalytic process.