methyl (RP)-(2′,6′-dimethoxybiphenyl-2-yl)(phenyl)-phosphinite P-borane | 1310457-33-0

• 英文名称: methyl (RP)-(2′,6′-dimethoxybiphenyl-2-yl)(phenyl)-phosphinite P-borane
• 英文别名: methyl (R_P)-(2′,6′-dimethoxybiphenyl-2-yl)(phenyl)-phosphinite P-borane；(R)-(2-(2',6'-dimethoxybiphenylyl))methoxyphenylphosphine-P-borane
• CAS: 1310457-33-0
• 化学式: C₂₁H₂₄BO₃P
• 分子量: 366.205
• InChiKey: MIQJUMAWUDILAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  methyl (RP)-(2′,6′-dimethoxybiphenyl-2-yl)(phenyl)-phosphinite P-borane 在 吗啉 作用下， 以 乙醚 为溶剂， 反应 14.5h， 生成 (S)-(2-(2',6'-dimethoxybiphenylyl))methylphenylphosphine
  参考文献：
  名称：

  P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

  摘要：

  Two groups of P-stereogenic monodentate phosphines containing pendant groups bearing functionalities capable of having secondary interactions, PArPhR (Ar = 2-[(2',6'-dimethoxy)-1,1'-biphenylyl] and R = OMe (6) or Me (8)) and PMeR(CH2R') (13, R t-Bu or 14 R Fc and R' SiMe3 (a), SiMe2Ph (b) or CH2(2-naphthyl) (c)) have been prepared in enantiomerically pure form by the Juge and Evans methodologies and characterised, including the crystal structure for the borane adduct of 12b. Reaction of the phosphines with the Pd dimer [Pd(eta(3)-2-Me-allyl)(mu-Cl)](2) produced neutral allylic complexes C [PdCl (eta(3)-2-Me-C3H4)P*], which have been characterised in solution and shown to be a mixture of isomers with different absolute configuration at the Pd atom. After abstraction of the chloride ligand by AgBF4, the solutions of cationic complexes have been used as catalyst precursors in the hydrovinylation of styrene under mild conditions. Very good activities (up to 1015 h(-1)), moderate to good selectivities to 3-phenyl-1-butene and low to moderate enantioselectivities (< 45% ee) have been found. Deep differences in the activity and enantioselectivity have been found depending on the structure of the ligand. In spite of that the results did not permit to confirm the improvement of the selectivities of the reaction by stabilization of the catalyst through secondary coordination with the potentially hemilabile ligands. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.02.034
• 作为产物：
  描述：

  2-溴氯苯 在 正丁基锂 、 硫酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 生成 methyl (RP)-(2′,6′-dimethoxybiphenyl-2-yl)(phenyl)-phosphinite P-borane
  参考文献：
  名称：

  P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene

  摘要：

  Two groups of P-stereogenic monodentate phosphines containing pendant groups bearing functionalities capable of having secondary interactions, PArPhR (Ar = 2-[(2',6'-dimethoxy)-1,1'-biphenylyl] and R = OMe (6) or Me (8)) and PMeR(CH2R') (13, R t-Bu or 14 R Fc and R' SiMe3 (a), SiMe2Ph (b) or CH2(2-naphthyl) (c)) have been prepared in enantiomerically pure form by the Juge and Evans methodologies and characterised, including the crystal structure for the borane adduct of 12b. Reaction of the phosphines with the Pd dimer [Pd(eta(3)-2-Me-allyl)(mu-Cl)](2) produced neutral allylic complexes C [PdCl (eta(3)-2-Me-C3H4)P*], which have been characterised in solution and shown to be a mixture of isomers with different absolute configuration at the Pd atom. After abstraction of the chloride ligand by AgBF4, the solutions of cationic complexes have been used as catalyst precursors in the hydrovinylation of styrene under mild conditions. Very good activities (up to 1015 h(-1)), moderate to good selectivities to 3-phenyl-1-butene and low to moderate enantioselectivities (< 45% ee) have been found. Deep differences in the activity and enantioselectivity have been found depending on the structure of the ligand. In spite of that the results did not permit to confirm the improvement of the selectivities of the reaction by stabilization of the catalyst through secondary coordination with the potentially hemilabile ligands. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.02.034

文献信息

• <i>P</i>-Stereogenic Phospholanes or Phosphorinanes from <i>o</i>-Biarylylphosphines: Two Bridges Not Too Far
  作者：Barbara Mohar、Alen Čusak、Barbara Modec、Michel Stephan

  DOI：10.1021/jo400565b

  日期：2013.5.17

  The discovery of a concise regiodivergent asymmetric route to nonclassical P-stereogenic 5- or 6-membered benzophosphacycles, under conditions-dependent radical (oxidative addition) versus anionic (SNAr) benzannulation, is reported.