7-ethyldinaphtho<2,1-b:1',2'-d>phosphole | 159211-64-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 7-ethyldinaphtho<2,1-b:1',2'-d>phosphole
• 英文别名: 12-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
• CAS: 159211-64-0；156854-48-7
• 化学式: C₂₂H₁₇P
• 分子量: 312.351
• InChiKey: KYYVIFRRZSWLLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  7-ethyldinaphtho<2,1-b:1',2'-d>phosphole 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以88%的产率得到7-ethyldinaphtho<2,1-b:1',2'-d>phosphole 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
• 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 7-ethyldinaphtho<2,1-b: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

• Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center
  作者：Liangzhi Pang、Qilin Sun、Zhan Huang、Gen Li、Jiaojiao Liu、Jiaxu Guo、Chuanzhi Yao、Jie Yu、Qiankun Li

  DOI：10.1002/anie.202211710

  日期：2022.11.21

  construction of atropisomers bearing a P-stereogenic center. The products are isolated in high yields with high diastereo- and enantioselectivities (>25 : 1 dr and up to 98 % ee). One of the isolated products is shown to catalyze the [3+2] cycloaddition of allenoates to imines, thus demonstrating the utility of the present methodology.

  在这里，我们报告了钯催化的 C-P 键立体选择性裂解，用于构建带有 P-立体中心的阻转异构体。产品以高非对映选择性和对映选择性（>25 : 1 dr 和高达 98% ee）高产率分离。其中一种分离的产物被证明可以催化联烯酸与亚胺的 [3+2] 环加成反应，从而证明了本方法的实用性。
• Binaphthyl-Substituted Chiral Phosphines and Oxides from Binaphthophooles and Nucleophiles
  作者：David Fabbri、Serafino Gladiali、Ottorino De Lucchi

  DOI：10.1080/00397919408011728

  日期：1994.5

  Binaphthophospholes 1 are the starting compounds for the synthesis of chiral phosphine oxides 3 or phosphines 4 via reaction of phospholium salts 2 with nucleophiles. The binaphthyl residue acts as a stereochemical probe for monitoring the integrity of the phosphorus stereocenter.
• Gladiali Serafino, Dore Antonio, Fabbri Davide, De Lucchi Ottorino, Valle+, J. Org. Chem, 59 (1994) N 21, S 6363-6371
  作者：Gladiali Serafino, Dore Antonio, Fabbri Davide, De Lucchi Ottorino, Valle+

  DOI：——

  日期：——
• 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.
• 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。