dinaphtho<2,1b:1',2'-d>phosphole

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dinaphtho<2,1b:1',2'-d>phosphole
• 英文别名: 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: C₂₀H₁₃P
• 分子量: 284.297
• InChiKey: RWNYGFGVSGGLAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  2,2-二溴-1,1-联萘 在 正丁基锂 、 lithium 作用下， 生成 dinaphtho<2,1b:1',2'-d>phosphole
  参考文献：
  名称：

  Dinaphtho[2,1-b; 1′,2′-d]phospholes: a new class of atropisomeric phosphorus ligands

  摘要：

  母体和一些烷基和芳基取代的二萘并[2,1-b； 1-,2-d]磷化合物 1 已被合成并显示在室温以下具有阻转异构性稳定。

  DOI：

  10.1039/c39930001124

文献信息

• One-pot synthesis of binaphthyl-based phosphines via direct modification of BINAP
  作者：Jing-Jing Ye、Jian-Qiu Zhang、Shigeru Shimada、Li-Biao Han

  DOI：10.1016/j.tetlet.2021.153489

  日期：2021.12

  Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to

  本文报道了通过用钠直接修饰市售的 2,2'-双(二苯基膦)-1,1'-联萘 (BINAP) 来制备联萘基膦的方便有效的策略。在没有 15-crown-5-ether 的情况下，主要生成环状二萘基磷酸钠中间体。使用 15-crown-5-ether 时，P-Ph 键被 Na 选择性裂解以产生基于联萘的磷化二钠。提出了选择性形成二萘基磷化钠或联萘基磷化二钠的机理。
• 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.
• Investigation of the Reductive Cleavage of BINAP and Application to the Rapid Synthesis of Phospholes
  作者：Chris W. D. Gallop、Mariusz Bobin、Petra Hourani、Jessica Dwyer、S. Mark Roe、Eddy M. E. Viseux

  DOI：10.1021/jo4006393

  日期：2013.7.5

  A rapid and easy entry into lambda(3)-phospholes and lambda(4)-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental P-31 resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism
• LIGANDS FOR METALS AND METAL-CATALYZED PROCESSES
  申请人：MASSACHUSETTS INSTITUTE OF TECHNOLOGY

  公开号：EP1097158B1

  公开（公告）日：2006-01-25
• Dinaphtho[2,1-b; 1′,2′-d]phospholes: a new class of atropisomeric phosphorus ligands
  作者：Antonio Dore、Davide Fabbri、Serafino Gladiali、Ottorino De Lucchi

  DOI：10.1039/c39930001124

  日期：——

  The parent and some alkyl and aryl substituted dinaphtho[2,1-b; 1′,2′-d]phospholes 1 have been synthesized and shown to be atropisomerically stable below room temperature.

  母体和一些烷基和芳基取代的二萘并[2,1-b； 1-,2-d]磷化合物 1 已被合成并显示在室温以下具有阻转异构性稳定。