(2-(1,1'-binaphthylyl))dimethylphosphine oxide | 159211-87-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2-(1,1'-binaphthylyl))dimethylphosphine oxide
• 英文别名: 2-dimethylphosphinyl-1,1'-binaphthyl；[2-(1,1'-binaphthylyl)]dimethylphosphine oxide；2-Dimethylphosphoryl-1-naphthalen-1-ylnaphthalene
• CAS: 159211-87-7
• 化学式: C₂₂H₁₉OP
• 分子量: 330.366
• InChiKey: ORTHPVDRSATHLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  (2-(1,1'-binaphthylyl))dimethylphosphine oxide 在 三氯硅烷 、 三乙胺 作用下， 以 xylene 为溶剂， 以88%的产率得到(S)-[1,1'-binaphthalen]-2-yldimethylphosphine
  参考文献：
  名称：

  磷化氢在铜（I）氢化酮催化的加氢反应中的作用以及α，β-不饱和酮和醛的区域选择性1,2-还原。十氢化萘和甾族酮及烯酮的氢化

  摘要：

  已经研究了使用可溶性氢化铜（I）催化剂催化酮和α，β-不饱和酮和醛催化氢化的立体选择性和区域选择性，它是辅助膦配体的函数。尽管相对窄范围的芳基二烷基膦配体产生活性氢化催化剂，但某些配体比使用先前报道的二甲基苯基膦稳定的催化剂观察到的对1,2-还原无环不饱和羰基底物的选择性更高。这类氢化氢化催化剂的合成用途可以通过十氢化萘和甾族酮和烯酮的氢化来说明，后者能提供高选择性的烯丙醇。

  DOI：

  10.1016/s0040-4020(00)00133-2
• 作为产物：
  描述：

  2,2-二溴-1,1-联萘 在 sodium hydroxide 、 正丁基锂 作用下， 以 二氯甲烷 为溶剂， 反应 20.5h， 生成 (2-(1,1'-binaphthylyl))dimethylphosphine oxide
  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

• Phosphine Effects in the Copper(I) Hydride-Catalyzed Hydrogenation of Ketones and Regioselective 1,2-Reduction of α,β-Unsaturated Ketones and Aldehydes. Hydrogenation of Decalin and Steroidal Ketones and Enones
  作者：Jian-Xin Chen、John F. Daeuble、Jeffrey M. Stryker

  DOI：10.1016/s0040-4020(00)00133-2

  日期：2000.4

  The stereoselectivity and regioselectivity of the catalytic hydrogenation of ketones and α,β-unsaturated ketones and aldehydes using soluble copper(I) hydride catalysts have been investigated as a function of the ancillary phosphine ligand. While a relatively narrow range of aryldialkylphosphine ligands produce active hydrogenation catalysts, some ligands provide higher selectivity for 1,2-reduction

  已经研究了使用可溶性氢化铜（I）催化剂催化酮和α，β-不饱和酮和醛催化氢化的立体选择性和区域选择性，它是辅助膦配体的函数。尽管相对窄范围的芳基二烷基膦配体产生活性氢化催化剂，但某些配体比使用先前报道的二甲基苯基膦稳定的催化剂观察到的对1,2-还原无环不饱和羰基底物的选择性更高。这类氢化氢化催化剂的合成用途可以通过十氢化萘和甾族酮和烯酮的氢化来说明，后者能提供高选择性的烯丙醇。
• 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.