1-iodo-8-diisopropylphosphinonaphthalene | 1428858-14-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-iodo-8-diisopropylphosphinonaphthalene
• 英文别名: (8-Iodonaphthalen-1-yl)-di(propan-2-yl)phosphane
• CAS: 1428858-14-3
• 化学式: C₁₆H₂₀IP
• 分子量: 370.213
• InChiKey: UOMSNGRIDFXYBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-iodo-8-diisopropylphosphinonaphthalene 在 正丁基锂 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 1.17h， 生成
  参考文献：
  名称：

  Diverse reactivity of borenium cations with >N–H compounds

  摘要：

  P-稳定的硼烷基阳离子1对>N–H化合物显示出丰富的反应性：与Ph₂NH发生取代反应，形成Lewis加合物并随后与NH₃脱质子化，B–Mes裂解并形成与HNTf₂的二阳离子物种。

  DOI：

  10.1039/c6cc03183h
• 作为产物：
  描述：

  1,8-二碘萘 、 氯二异丙基膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以45%的产率得到1-iodo-8-diisopropylphosphinonaphthalene
  参考文献：
  名称：

  Phosphino-Boryl-Naphthalenes: Geometrically Enforced, Yet Lewis Acid Responsive P → B Interactions

  摘要：

  Three naphthyl-bridged phosphine-borane derivatives 2-BCy2, 2-BMes(2) and 2-BFlu, differing in the steric and electronic properties of the boryl moiety, have been prepared and characterized by spectroscopic and crystallo-graphic means. The presence and magnitude of the P -> B interactions have been assessed experimentally and theoretically. The naphthyl linker was found to enforce the P -> B interaction despite steric shielding, while retaining enough flexibility to respond to the Lewis acidity of boron.

  DOI：

  10.1021/ic4003466

文献信息

• Cu-Catalyzed P–C bond formation/cleavage: straightforward synthesis/ring-expansion of strained cyclic phosphoniums
  作者：Maryne Duval、Charlie Blons、Sonia Mallet-Ladeira、Damien Delcroix、Lionel Magna、Hélène Olivier-Bourbigou、E. Daiann Sosa Carrizo、Karinne Miqueu、Abderrahmane Amgoune、György Szalóki、Didier Bourissou

  DOI：10.1039/d0dt03059g

  日期：——

  observations and DFT calculations, two mechanistic pathways are operating: (i) direct oxidative addition of the strained P–C bond to gold,(ii) backward-formation of the peri-halo naphthyl phosphine (by C–P oxidative addition to copper followed by C–X reductive elimination), copper to gold exchange and oxidative addition of the C–X bond to gold. Detailed analysis of the reaction profiles computed theoretically

  在与铜反应（我），围卤代萘基膦容易地形成围-bridged萘基鏻盐。该反应与磷处的烷基，芳基和氨基取代基一起起作用，碘，溴和氯为卤素。尽管与所得的四元环结构和萘骨架有关，但是它在温和的条件下进行并且是定量的。该转化适合催化。在优化条件下，该关节周围碘萘基膦1-I被转换成相应的周围-bridged萘基鏻盐2b中使用1 mol％的CuI在室温下仅需5分钟。根据DFT计算，提出该反应涉及一个由P-配位，C–X氧化加成和P–C还原消除组成的Cu（I）/ Cu（III）循环。该铜-催化的路线给予一般的和有效的访问围首次-bridged萘基鏻盐。因此可以启动反应性研究，并证明了将金插入应变的PC键中的可能性。生成（P，C）-环金属化金（III）配合物。据实验观察和DFT计算两个机制途径正在操作：（ⅰ）直接氧化加成应变P-C键的金的，（ii）所述的向后形成围-卤代萘基膦（通过C–P氧化加成至铜，然后C–
• Formation of a <i>peri</i> ‐Bridged Phosphonio‐Naphthalene by Cu‐Mediated Phosphine–Aryl Coupling
  作者：Charlie Blons、Maryne Duval、Damien Delcroix、Hélène Olivier‐Bourbigou、Sonia Mallet‐Ladeira、E. Daiann Sosa Carrizo、Karinne Miqueu、Abderrahmane Amgoune、Didier Bourissou

  DOI：10.1002/chem.201802579

  日期：2018.8.14

  The peri‐iodo naphthyl phosphine 1 reacts with CuI to give the peri‐bridged phosphonio‐naphthalene 2, which has been fully characterized (multi‐nuclear NMR, MS, XRD). The outcome of the reaction differs markedly from that observed with gold. A two‐step pathway involving P‐assisted C−I oxidative addition to copper, followed by P−C reductive elimination is shown to be energetically feasible by DFT calculations

  所述围碘萘基膦1下进行反应与碘化亚铜，得到围-bridged phosphonio萘2，这已被充分表征（多核NMR，MS，XRD）。反应的结果与金观察到的结果明显不同。通过DFT计算，从能量上讲，通过两步途径将P辅助C–I氧化添加到铜中，然后进行P–C还原消除是可行的。
• Cationic Gold(III) Alkyl Complexes: Generation, Trapping, and Insertion of Norbornene
  作者：Feriel Rekhroukh、Rémy Brousses、Abderrahmane Amgoune、Didier Bourissou

  DOI：10.1002/anie.201409604

  日期：2015.1.19

  been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C6F5)3 is shown to generate a highly reactive cationic AuIII complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the AuC bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to

  从离散的（P，C）环金属化的金（III）二甲基络合物中研究了烯烃向金-碳键中的迁移插入，这是一个前所未有的基础性有机金属转化。通过B（C 6 F 5）3提取甲硫氨酸可产生高反应性的阳离子Au III络合物，该络合物通过从硼中转移C 6 F 5自发形成。在降冰片烯的存在下，向AuC键的迁移容易进行。生成的降冰片基络合物有效地被吡啶或氯化物截留，得到稳定的四配位加合物。
• Amino and Alkyl B-Substituted P-Stabilized Borenium Salts
  作者：Marc Devillard、Ghenwa Bouhadir、Sonia Mallet-Ladeira、Karinne Miqueu、Didier Bourissou

  DOI：10.1021/acs.organomet.6b00737

  日期：2016.11.14

  The ability of the phosphino-naphthyl moiety to stabilize amino- and alkylborenium cations has been studied. Surprisingly, the phosphine-aminochloroborane precursor 2 was found to exist in neutral open form (without P -> B interaction) in benzene solution and in the solid state but to ionize spontaneously in chloroform to generate the P-stabilized borenium salt 3. Addition of gallium trichloride shifts the process forward and affords the corresponding tetrachlorogallate borenium salt 3'. The phosphine group of 2 remains available for external reactivity, as shown by the ready formation of the corresponding phosphine gold(I) chloride complex 4. The P-stabilized cyclohexylborenium cation 6 has also been prepared by reacting the corresponding bromoborane 5 with gallium tribromide. Compound 6 is a very rare example of an alkyl-substituted borenium salt. The structures of 2, 3', and 4-6 have been unambiguously ascertained by multinuclear NMR spectroscopy and X-ray crystallography.
• Silver-mediated intramolecular P–C coupling
  作者：György Szalóki、Karinne Miqueu、Didier Bourissou

  DOI：10.1016/j.mencom.2022.01.025

  日期：2022.1