(E)-1-(diphenylphosphinyl)-1-heptene | 100585-48-6

• 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: (E)-1-(diphenylphosphinyl)-1-heptene
• 英文别名: (E)-hept-1-en-1-yldiphenylphosphine oxide；[[(E)-hept-1-enyl]-phenylphosphoryl]benzene
• CAS: 100585-48-6
• 化学式: C₁₉H₂₃OP
• 分子量: 298.365
• InChiKey: BOZVPTUPXHJOHH-SFQUDFHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-1-(diphenylphosphinyl)-1-heptene 、 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物 反应 1.0h， 以80%的产率得到1-diphenylphosphinyl-2-(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)heptane
  参考文献：
  名称：

  Microwave-Assisted Regioselective Addition of P(O)−H Bonds to Alkenes without Added Solvent or Catalyst

  摘要：

  The addition of P(O)-H bonds to alkenes has been accomplished using microwave irradiation in the absence of added solvent and catalyst. In addition to single addition reactions, tandem hydrophosphinylation reactions with alkynes afforded unsymmetrical species such as phosphine oxide - phosphinates.

  DOI：

  10.1021/ol0474047
• 作为产物：
  描述：

  2-辛炔酸 、 Diphenylphosphine oxide 在 copper(l) chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以30%的产率得到(E)-1-(diphenylphosphinyl)-1-heptene
  参考文献：
  名称：

  Copper-Catalyzed Decarboxylative C–P Cross-Coupling of Alkynyl Acids with H-Phosphine Oxides: A Facile and Selective Synthesis of (E)-1-Alkenylphosphine Oxides

  摘要：

  A novel and efficient copper-catalyzed decarboxylative cross-coupling of alkynyl acids for the stereoselective synthesis of E-alkenylphosphine oxides has been developed. In the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and the stereoselectivity for E-isomers.

  DOI：

  10.1021/ol502009b

文献信息

• Z-Selective Addition of Diaryl Phosphine Oxides to Alkynes via Photoredox Catalysis
  作者：Huamin Wang、Yongli Li、Zilu Tang、Shengchun Wang、Heng Zhang、Hengjiang Cong、Aiwen Lei

  DOI：10.1021/acscatal.8b02617

  日期：2018.11.2

  Radical addition to alkynes is known to predominantly yield thermodynamically more stable E-alkenes. Control of stereoselectivity in these reactions, and the isolation of the higher-energy Z-alkenes, remain an important challenge in chemical synthesis. Herein, direct synthesis of Z-alkenylphosphine oxides via visible-light-induced radical addition to alkynes in water is reported. This protocol was

  已知向炔烃中自由基加成主要产生热力学上更稳定的E-烯烃。这些反应中立体选择性的控制以及高能Z-烯烃的分离仍然是化学合成中的重要挑战。本文中，报道了通过可见光诱导的自由基加成至水中的炔烃直接合成Z-烯基膦氧化物。该方案对各种末端和内部炔烃均有效，可提供具有高Z-立体选择性的产物。此外，这种转化以克为单位进行了证明。机理研究支持以下结论：（1）通过自由基加成反应。（2）K 2 CO 3的选择因为水性碱对转化至关重要；（3）π–π堆积相互作用极大地提高了Z选择性。
• Copper-catalyzed stereo- and regioselective hydrophosphorylation of terminal alkynes: scope and mechanistic study
  作者：Junchen Li、Zhenhua Gao、Yongbiao Guo、Haibo Liu、Peichao Zhao、Xiaojing Bi、Enxue Shi、Junhua Xiao

  DOI：10.1039/d2ra02908a

  日期：——

  highly stereo- and regioselective hydrophosphorylation of terminal alkynes to E-alkenylphosphorus compounds was well developed. It represents a general and practical hydrophosphorylation method, of which diarylphosphine oxide, dialkylphosphine oxide and dialkyl phosphite all had effective P(O)H parts to react with different types of terminal alkynes. Contrary to previous air-sensitive reports, all the reactions

  在这里，铜催化的末端炔烃到 E-烯基磷化合物的高度立体和区域选择性氢化磷酸化的协议得到了很好的发展。它代表了一种通用且实用的氢化磷酸化方法，其中二芳基氧化膦、二烷基氧化膦和亚磷酸二烷基酯均具有有效的P(O)H部分与不同类型的末端炔烃反应。与之前对空气敏感的报道相反，所有反应都在空气中进行。由于某些天然产物衍生物和市售除草剂的高立体选择性和区域选择性、良好的官能团耐受性、可扩展性和易于后期衍生化，这种方法非常有吸引力。更重要的是，
• Solovetskaya, L. A.; Sergeev, N. M.; Magdeeva, R. K., Journal of general chemistry of the USSR, 1985, vol. 55, # 5, p. 1072 - 1073
  作者：Solovetskaya, L. A.、Sergeev, N. M.、Magdeeva, R. K.、Nifant'ev, E. E.

  DOI：——

  日期：——
• Nifant'ev, E. E.; Solovetskaya, L. A.; Magdeeva, R. K., Journal of general chemistry of the USSR, 1985, vol. 55, p. 2010 - 2015
  作者：Nifant'ev, E. E.、Solovetskaya, L. A.、Magdeeva, R. K.

  DOI：——

  日期：——
• Tandem Peterson-Michael Reaction Using a-Silylalkylphosphine Chalcogenides and Horner-Emmons Reaction of in situ Generated a-Carbanions of Its Products
  作者：Takayuki Kawashima、Mio Nakamura、Naoki Inamoto

  DOI：10.3987/com-96-s49

  日期：——

  Title tandem reaction was achieved by using alpha-(trimethylsilyl)alkylphosphine chalcogenides and the lithio derivative of 2-hydroxytetrahydropyran. The Horner-Emmons reaction of the tandem products was accomplished to give the corresponding 2-(beta-styryl)tetrahydropyran derivatives by in situ generation and trapping of alpha-lithio derivatives, followed by Warren's method of olefination.