1-(iso-butyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene | 1151508-87-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(iso-butyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene
• 英文别名: 3,4,5-triphenyl-1-isobutyl-1,2-diphosphacyclopenta-2,4-diene；1-(2-methylpropyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene；1-(2-Methylpropyl)-3,4,5-triphenyldiphosphole
• CAS: 1151508-87-0
• 化学式: C₂₅H₂₄P₂
• 分子量: 386.413
• InChiKey: ACTCXFXGEZZEDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.16
• 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-(iso-butyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene 在 N-叔丁基-α-苯基硝酮 作用下， 生成 C₅₀H₄₈O₂P₄
  参考文献：
  名称：

  Versatile Cycloaddition Reactions of 1-Alkyl-1,2-Diphospholes

  摘要：

  The reactivity of 1-alkyl-1,2-diphospholes in cycloaddition reactions with dienes, dienophiles or 1,3-dipoles was examined. 1-Alkyl-1,2-diphospholes (2 ) exhibit dual reactivity and act as diene toward maleic acid derivatives or as dienophiles with 2,3-dimethyl-1,3-butadiene. The 1-alkenyl-1,2-diphospholes (4 )are readily involved in intramolecular [4 + 2] cycloaddition reactions leading to cage phosphines (5 ). Interaction of 1-alkyl-1,2-diphospholes (2) with 1,3-dipolar reagents (diphenyldiazomethane and nitrones) results in formation of the bicyclic phosphiranes (8) and dimers of 1-alkyl-1,2-diphosphole oxides (9) or bicyclic phosphine oxides (10) with a -lactam moiety depending on temperature.

  DOI：

  10.1080/10426507.2012.744017
• 作为产物：
  描述：

  sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide 、 溴代异丁烷 以 四氢呋喃 为溶剂， 以55%的产率得到1-(iso-butyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene
  参考文献：
  名称：

  1-烷基-3,4,5-三苯基-1,2-二磷酸环戊基-2,4-二烯的环加成反应

  摘要：

  1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes 1，由 1,2-diphospha-3,4,5-triphenylcyclopentadienide 钠烷基化获得，在环加成反应中表现出双重反应性：作为二烯（与马来酸酐和马来酰亚胺）或作为亲二烯体（与 2,3-二甲基丁二烯）。1 的热解发生 [1,5] σ 迁移，形成 [2+2] 环二聚产物。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2009）

  DOI：

  10.1002/ejoc.200801181

文献信息

• Cycloaddition reactions of 1-Alkyl-3,4,5-triphenyl-1,2-iphosphacyclopenta-2,4-dienes in the coordination sphere of tungsten carbonyl
  作者：V. A. Milyukov、A. A. Zagidullin、E. Hey-Hawkins、O. G. Sinyashin

  DOI：10.1134/s1070328410120043

  日期：2010.12

  1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes react with tungsten hexacarbonyl under the conditions of “indirect” replacement of the carbonyl group to give 1: 1 complexes; [4+2] cycloaddition reactions of these complexes with maleic acid derivatives and substituted acetylenes afford tungsten carbonyl complexes containing 10-alkyl-1,10-diphosphatricyclo[5.2.1.02.6]deca-8-ene-3,5-diones

  在“间接”取代羰基的条件下，1-烷基-3,4,5-三苯基-1,2-二磷杂环戊-2,4-二烯与六羰基钨反应，形成1：1络合物；这些配合物与马来酸衍生物和取代的乙炔的[4 + 2]环加成反应得到羰基钨配合物，该配合物含有10-烷基-1,10-二磷三环[5.2.1.0 2.6 ] deca-8-ene-3,5-diones和1 -烷基-2，3-二苯基膦基。
• Reactions of sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide with alkyl halides and silicon and tin chlorides
  作者：V. A. Milyukov、I. A. Bezkishko、A. A. Zagidullin、O. G. Sinyashin、E. Hey-Hawkins

  DOI：10.1007/s11172-010-0226-9

  日期：2010.6

  Reactions of sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide with primary alkyl bromides, secondary alkyl iodides, and silicon and tin chlorides gave stable 1-substituted 1,2-diphospholes. In a solution of 3,4,5-triphenyl-1-trimethylstannyl-1,2-diphosphacyclopenta-2,4-diene, the Me3Sn group migrates between two phosphorus atoms.

  3,4,5-三苯基-1,2-二磷酸环戊二烯钠与伯烷基溴、仲烷基碘以及硅和氯化锡的反应得到稳定的1-取代的1,2-二磷。在 3,4,5-triphenyl-1-trimethylstannyl-1,2-diphosphacyclopenta-2,4-diene 的溶液中，Me3Sn 基团在两个磷原子之间迁移。
• <i>P</i>-Chiral 1,7-diphosphanorbornenes: from asymmetric phospha-Diels–Alder reactions towards applications in asymmetric catalysis
  作者：A. A. Zagidullin、E. S. Oshchepkova、I. V. Chuchelkin、S. A. Kondrashova、V. A. Miluykov、Sh. K. Latypov、K. N. Gavrilov、E. Hey-Hawkins

  DOI：10.1039/c9dt00443b

  日期：——

  A straightforward synthesis of P-chiral polycyclic phosphines by an asymmetric Diels–Alder reaction of 1-alkyl-1,2-diphospholes and (5R)-(L-menthyloxy)-2(5H)-furanone (MOxF) is presented. The [4 + 2] cycloaddition reaction of 1,2-diphospholes 1–3 with MOxF (4) proceeded with high diastereoselectivity (de up to 90%) resulting in the corresponding enantiopure anti-endo-1,7-diphosphanorbornenes 5a–7a

  提出了一种通过1-烷基-1，2-二苯基和（5 R）-（L-薄荷氧基）-2（5 H）-呋喃酮（MOxF）的不对称Diels-Alder反应直接合成P-手性多环膦的方法。。1,2-二磷1-3与MOxF的[4 + 2]环加成反应（4）具有很高的非对映选择性（高达90％），从而产生了相应的对映体纯的抗内源-1,7-二磷杂降冰片5a-7a。通过各种1D / 2D NMR相关方法证明了5-7的绝对构型。使用的抗内-diphosphanorbornene -1,7- 5A在Pd催化的肉桂酸乙酸肉桂酯8的不对称烯丙基烷基化反应中，用环状β-酮酯9a，b提供高达52％的ee。
• Cycloaddition Reactions of 1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes
  作者：Vasili Miluykov、Ilya Bezkishko、Almaz Zagidullin、Oleg Sinyashin、Peter Lönnecke、Evamarie Hey-Hawkins

  DOI：10.1002/ejoc.200801181

  日期：2009.3

  1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes 1, obtained by alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide, exhibit dual reactivity in cycloaddition reactions: as dienes (with maleic anhydride and maleimide) or as dienophiles (with 2,3-dimethylbutadiene). Thermolysis of 1 occurs with a [1,5] sigmatropic shift to form a [2+2] cyclodimerization product.(© Wiley-VCH

  1-Alkyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-dienes 1，由 1,2-diphospha-3,4,5-triphenylcyclopentadienide 钠烷基化获得，在环加成反应中表现出双重反应性：作为二烯（与马来酸酐和马来酰亚胺）或作为亲二烯体（与 2,3-二甲基丁二烯）。1 的热解发生 [1,5] σ 迁移，形成 [2+2] 环二聚产物。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2009）
• Versatile Cycloaddition Reactions of 1-Alkyl-1,2-Diphospholes
  作者：Almaz Zagidullin、Yulia Ganushevich、Vasili Miluykov、Oleg Sinyashin、Evamarie Hey-Hawkins

  DOI：10.1080/10426507.2012.744017

  日期：2013.1.1

  The reactivity of 1-alkyl-1,2-diphospholes in cycloaddition reactions with dienes, dienophiles or 1,3-dipoles was examined. 1-Alkyl-1,2-diphospholes (2 ) exhibit dual reactivity and act as diene toward maleic acid derivatives or as dienophiles with 2,3-dimethyl-1,3-butadiene. The 1-alkenyl-1,2-diphospholes (4 )are readily involved in intramolecular [4 + 2] cycloaddition reactions leading to cage phosphines (5 ). Interaction of 1-alkyl-1,2-diphospholes (2) with 1,3-dipolar reagents (diphenyldiazomethane and nitrones) results in formation of the bicyclic phosphiranes (8) and dimers of 1-alkyl-1,2-diphosphole oxides (9) or bicyclic phosphine oxides (10) with a -lactam moiety depending on temperature.