1,2-bis-(binaphtho<2,1-b;1',2'-d>phospholyl)ethane

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,2-bis-(binaphtho<2,1-b;1',2'-d>phospholyl)ethane
• 英文别名: 1,2-bis(dinaphtho<2,1-b:1',2'-d>phospholyl)ethane；1,2-bis(dinaphtho[2,1-b:1',2'-d]phospholyl)ethane；12-[2-(12-Phosphapentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaen-12-yl)ethyl]-12-phosphapentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaene
• 化学式: C₄₂H₂₈P₂
• 分子量: 594.632
• InChiKey: FFJNNBXMTXOKLQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.3
• 重原子数：
  44
• 可旋转键数：
  3
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  3,3',4,4'-四氢-1,1'-联萘 在 氯代叔丁烷 、 lithium 作用下， 反应 15.0h， 生成 1,2-bis-(binaphtho<2,1-b;1',2'-d>phospholyl)ethane
  参考文献：
  名称：

  Synthesis, Crystal Structure, Dynamic Behavior and Reactivity of Dinaphtho[2,1-b:1',2'-d]phospholes and Related Atropisomeric Phosphacyclic Derivatives

  摘要：

  7-Phenyldinaphtho[2,1-b:1',2'-d]phosphole (1b) has been prepared by reaction of dichlorophenylphosphine either with 2,2'-dilithio-1,1'-binaphthalene or with bis-dialin 7. In the latter case the relevant tetrahydro derivative 8 is formed at the same time. Displacement of the phenyl substituent in Ib by alkyl groups can be accomplished through a dephenylation-alkylation protocol involving a lithium-promoted phosphole anion formation. By this way the unsubstituted phosphole la and a variety of alkyl-substituted derivatives have been prepared. The X-ray crystal structure of Ib shows an intracyclic C-P-C angle of 89.3 degrees indicating that phosphole ring is strained. Alkylphospholium iodides 4 undergo ready ring opening by reaction with LiAlH4 or other nucleophiles under mild conditions affording with fair diastereoselectivities (2-(1,1'-binaphthylyl))substituted phosphines 5 or phosphines oxides 6, respectively. Dinaphthophospholes 1 are fluxional at ambient temperature because of the rapid interconversion of the atropisomeric conformers. Line shape analysis of the variable temperature NMR spectra lead to estimation of an energy barrier of 55-60 kJ mol(-1) for this process. Fluxionality is maintained both when the phosphorus center is tetrasubstituted, like in the relevant oxides 2, and when it is coordinated to a transition metal, like in the Pd-complexes 10. On the contrary, P-substituted dinaphthophosphepines 9 do not undergo atropisomerization even well above room temperature and can be successfully resolved under ambient conditions. The crystal structures of the P-phenyl-substituted derivatives 1b, 8 and 9a, as determined by X-ray diffraction, show remarkable differences in the relative disposition of the naphthalene rings.

  DOI：

  10.1021/jo00100a044

文献信息

• Asymmetric hydroformylation of styrene catalysed by platinum-tin complexes with chiral bis-binaphthophosphole ligands
  作者：Serafino Gladiali、Davide Fabbri、Làszlò Kollar

  DOI：10.1016/0022-328x(94)05253-8

  日期：1995.4

  reaction of the bis(BNP) compounds with platinum(II) derivatives gives either cis chelate mononuclear complexes or trans phosphorus-bridged polynuclear derivatives. The latter can be converted into the mononuclear species by warming them in the presence of SnCl2. Coordination to platinum enhances the conformational stability of 3 and 4 and separate diastereomeric complexes can be detected in solution up to

  一组新颖的二齿的配位体2，3和4，已经合成，其具有两个轴向手性binaphthophospholyl（BNP）通过不同长度（2〜4个原子）的碳链连接的取代基通过与合适的二碘化物或烷基化的binaphthophospholyl阴离子二甲苯磺酸酯。在溶液中，由于二萘基骨架易于进行阻转异构化，所以游离的二磷脂表现出通量行为。根据其结构，双（BNP）化合物与铂（II）衍生物的反应生成顺式螯合单核络合物或反式磷桥联的多核衍生物。后者可以通过在SnCl 2的存在下加热使其转化为单核物质。与铂的配位可增强3和4的构象稳定性，并且可以在最高约50°C的溶液中检测到单独的非对映异构体。在SnCl 2的存在下，含有3和4的铂络合物产生了在苯乙烯的加氢甲酰化中表现出显着活性的催化剂。在最佳条件下，发生的反应具有前所未有的高分支选择性（80％-5％）和中等对映选择性（最高45％ee）。
• Synthesis, Crystal Structure, Dynamic Behavior and Reactivity of Dinaphtho[2,1-b:1',2'-d]phospholes and Related Atropisomeric Phosphacyclic Derivatives
  作者：Serafino Gladiali、Antonio Dore、Davide Fabbri、Ottorino De Lucchi、Giovanni Valle

  DOI：10.1021/jo00100a044

  日期：1994.10

  7-Phenyldinaphtho[2,1-b:1',2'-d]phosphole (1b) has been prepared by reaction of dichlorophenylphosphine either with 2,2'-dilithio-1,1'-binaphthalene or with bis-dialin 7. In the latter case the relevant tetrahydro derivative 8 is formed at the same time. Displacement of the phenyl substituent in Ib by alkyl groups can be accomplished through a dephenylation-alkylation protocol involving a lithium-promoted phosphole anion formation. By this way the unsubstituted phosphole la and a variety of alkyl-substituted derivatives have been prepared. The X-ray crystal structure of Ib shows an intracyclic C-P-C angle of 89.3 degrees indicating that phosphole ring is strained. Alkylphospholium iodides 4 undergo ready ring opening by reaction with LiAlH4 or other nucleophiles under mild conditions affording with fair diastereoselectivities (2-(1,1'-binaphthylyl))substituted phosphines 5 or phosphines oxides 6, respectively. Dinaphthophospholes 1 are fluxional at ambient temperature because of the rapid interconversion of the atropisomeric conformers. Line shape analysis of the variable temperature NMR spectra lead to estimation of an energy barrier of 55-60 kJ mol(-1) for this process. Fluxionality is maintained both when the phosphorus center is tetrasubstituted, like in the relevant oxides 2, and when it is coordinated to a transition metal, like in the Pd-complexes 10. On the contrary, P-substituted dinaphthophosphepines 9 do not undergo atropisomerization even well above room temperature and can be successfully resolved under ambient conditions. The crystal structures of the P-phenyl-substituted derivatives 1b, 8 and 9a, as determined by X-ray diffraction, show remarkable differences in the relative disposition of the naphthalene rings.