r-1,trans-2(e),6(e)-triphenyl-4-phosphorinanone

• 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: r-1,trans-2(e),6(e)-triphenyl-4-phosphorinanone
• 英文别名: 1,2,6-Triphenyl-4-oxo-phosphorinan；1,2,6-Triphenyl-phosphacyclohexan-4-on；1.2.6-Triphenyl-phosphorinanon-(4)；1,2,6-triphenyl-4-phosphorinanone；1,2,6-triphenyl-phosphinan-4-one；1,2,6-triphenylphosphinan-4-one
• 化学式: C₂₃H₂₁OP
• 分子量: 344.393
• InChiKey: LQWINIIHGWXQCK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  r-1,trans-2(e),6(e)-triphenyl-4-phosphorinanone 在 sodium hydroxide 、 一水合肼 作用下， 以 二乙二醇 为溶剂， 生成 1.2.6-Triphenyl-phosphorinan
  参考文献：
  名称：

  4-Phosphorinanones. II

  摘要：

  DOI：

  10.1021/jo01052a083
• 作为产物：
  描述：

  二苄叉丙酮 、 苯基膦 反应 0.22h， 生成 r-1,trans-2(e),6(e)-triphenyl-4-phosphorinanone
  参考文献：
  名称：

  4-Phosphorinanones. II

  摘要：

  DOI：

  10.1021/jo01052a083

文献信息

• Bulky 4-phosphacyclohexanones: diastereoselective complexations, orthometallations and unprecedented [3.1.1]metallabicycles
  作者：Ruth Doherty、Mairi F. Haddow、Zo? A. Harrison、A. Guy Orpen、Paul G. Pringle、Alex Turner、Richard L. Wingad

  DOI：10.1039/b607490a

  日期：——

  The 4-phosphacyclohexanones, 2,2,6,6-tetramethyl-1-phenyl-4-phosphorinanone (La), 1,2,6-triphenyl-4-phosphorinanone (PhLb), 1-cyclohexyl-2,6-diphenyl-4-phosphorinanone (CyLb) and 1-tert-butyl-2,6-diphenyl-4-phosphorinanone (BuLb) have been made by modifications of literature methods. Phosphines RLb are each formed as mixtures of meso- and rac-diastereoisomers. Isomerically pure rac-PhLb, rac-CyLb and meso-BuLb can be isolated by recrystallisation from MeCN. Heating mixtures of isomers of RLb with TsOH leads to isomerisations to give predominantly the meso-RLb. The complex trans-[PdCl2(La)2] (1) is readily made from [PdCl2(NCPh)2] but the analogous platinum complex 2 has not been detected and instead, cyclometallation at the 3-position (α to the ketone) in the phosphacycle occurs to give trans-[PtCl(La)(La–3H)] (3) (where La–3H = La deprotonated at the 3-position) featuring a [3.1.1]metallabicycle as confirmed by X-ray crystallography. The analogous palladabicycle 4 has been detected upon treatment of 1 with Et3N in refluxing toluene. The type of complex formed by RLb depends on which diastereoisomer (meso or rac) is involved. rac-PhLb (a mixture of R,R- and S,S-enantiomers, labelled α and β) forms trans-[MCl2(rac-PhLb)2], M = Pd (5) or Pt (6), as mixtures of diastereoisomers (αα/ββ and αβ forms). The structure of αα-6 has been determined by X-ray crystallography. Ligand competition experiments monitored by 31P NMR showed that Pd(II) and Pt(II) have a significant preference to bind rac-PhLb over meso-PhLb. meso-BuLb reacts with [PtCl2(NCBut)2] under ambient conditions to give the binuclear complex [Pt2Cl2(meso-BuLb-2′H)2] (7) where orthometallation has occurred on one of the exocyclic phenyl substituents as confirmed by X-ray crystallography. rac-BuLb reacts with [PtCl2(NCBut)2] to give a mononuclear cyclometallated species assigned the structure trans-[PtCl(rac-BuLb-2′H)(BuLb)] (8) on the basis of its 31P NMR spectrum. rac-CyLb reacts with [PtCl2(NCBut)2] in refluxing toluene to give trans-[PtCl2(rac-CyLb)2] (9) and the crystal structure of αβ-9 has been determined.

  4-phosphacyclohexanones, 2,2,6,6-tetramethyl-1-phenyl-4-phosphorinanone (La), 1,2,6-triphenyl-4-phosphorinanone (PhLb), 1-cyclohexyl-2,6-diphenyl-4-phosphorinanone (CyLb) 和 1-tert-butyl-2,6-diphenyl-4-phosphorinanone (BuLb) 是通过修改文献方法制成的。磷化物 RLb 分别以中对映异构体和rac-对映异构体混合物的形式形成。通过从 MeCN 中重结晶，可以分离出异构纯的 rac-PhLb、rac-CyLb 和 meso-BuLb。用 TsOH 加热 RLb 异构体的混合物会导致异构化，主要生成中-RLb。反式-[PdCl2(La)2] (1) 复合物很容易从[PdCl2(NCPh)2]制得，但类似的铂复合物 2 还没有被检测到，相反，在磷环的 3 位（酮的 α 位）发生环金属化反应，得到反式-[PtCl(La)(La-3H)] (3) （其中 La-3H = La 在 3 位去质子化），具有 [3.1.1]金属杂环，这一点已得到 X 射线晶体学的证实。在回流甲苯中用 Et3N 处理 1 时，也检测到了类似的金属杂环 4。rac-PhLb（R,R- 和 S,S-对映体的混合物，标记为 α 和 β）形成反式-[MCl2(rac-PhLb)2]，M = Pd (5) 或 Pt (6)，为非对映异构体的混合物（αα/ββ 和 αβ 形式）。αα-6的结构已通过X射线晶体学确定。通过 31P NMR 监测的配体竞争实验表明，钯（II）和铂（II）更倾向于结合 rac-PhLb，而不是 meso-PhLb。介-BuLb 在环境条件下与 [PtCl2(NCBut)2]反应，生成双核复合物 [Pt2Cl2(介-BuLb-2′H)2]（7），X 射线晶体学证实，其中一个外环苯基取代基发生了正金属化反应。rac-BuLb 与 [PtCl2(NCBut)2]反应，生成一种单核环金属物种，根据其 31P NMR 光谱，其结构为反式-[PtCl(rac-BuLb-2′H)(BuLb)] (8)。rac-CyLb 与 [PtCl2(NCBut)2]在回流甲苯中反应生成反式-[PtCl2(rac-CyLb)2]（9），并确定了 αβ-9 的晶体结构。
• Maerkl,G.; Olbrich,H., Tetrahedron Letters, 1968, p. 3813 - 3816
  作者：Maerkl,G.、Olbrich,H.

  DOI：——

  日期：——
• Maerkl,G. et al., Tetrahedron Letters, 1970, p. 645 - 648
  作者：Maerkl,G. et al.

  DOI：——

  日期：——
• Palladacycle-Catalyzed Asymmetric Intermolecular Construction of Chiral Tertiary P-Heterocycles by Stepwise Addition of H–P–H Bonds to Bis(enones)
  作者：Yinhua Huang、Sumod A. Pullarkat、Siewping Teong、Renta Jonathan Chew、Yongxin Li、Pak-Hing Leung

  DOI：10.1021/om300405h

  日期：2012.7.9

  A palladacycle-catalyzed diastereo- and enantio-selective stepwise double hydrophosphination of bis(enones) with PhPH2 has been developed, allowing intermolecular construction of chiral tertiary bulky P-heterocycles in one pot in high yields. A catalytic cycle for the reaction is proposed as well.
• PHOSPHACYCLOHEXANE UND IHRE VERWENDUNG IN DER HYDROFORMYLIERUNG VON OLEFINEN
  申请人：BASF SE

  公开号：EP1296992B1

  公开（公告）日：2008-04-23