2-(di-o-tolylphosphino)phenol | 254441-31-1

• 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: 2-(di-o-tolylphosphino)phenol
• 英文别名: 2-Bis(2-methylphenyl)phosphanylphenol
• CAS: 254441-31-1
• 化学式: C₂₀H₁₉OP
• 分子量: 306.344
• InChiKey: KYLIOHCCEWZLTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-乙酰甘氨酸 、 2-(di-o-tolylphosphino)phenol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 以32%的产率得到N-acetylglycine 2-(di-o-tolylphosphino)phenol ester
  参考文献：
  名称：

  Controlled oxidative addition of amino acid esters to Rh(I)

  摘要：

  The new sterically demanding phosphine 2-(di-o-tolylphosphino)phenol was prepared and used to create a series of esters with N-acylated amino acids. The phosphine-containing esters react within 30-60 min at room temperature with [(mu-Cl)Rh(cyclooctene)(2)](2) to give products of oxidative addition of the ester carbonyl-oxygen bond to the Rh center. The N-acyl carbonyl oxygen is bound to the Rh in these initial adducts, but is displaced upon addition of PMe3. Remarkably, both initial products and their PMe3 adducts are formed as single five-coordinate diastereomers in essentially quantitative yields. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00311-3
• 作为产物：
  描述：

  1-(甲氧基甲氧基)苯 在 盐酸 、 叔丁基锂 作用下， 以 甲醇 、 乙醚 、 正己烷 为溶剂， 反应 39.0h， 生成 2-(di-o-tolylphosphino)phenol
  参考文献：
  名称：

  Controlled oxidative addition of amino acid esters to Rh(I)

  摘要：

  The new sterically demanding phosphine 2-(di-o-tolylphosphino)phenol was prepared and used to create a series of esters with N-acylated amino acids. The phosphine-containing esters react within 30-60 min at room temperature with [(mu-Cl)Rh(cyclooctene)(2)](2) to give products of oxidative addition of the ester carbonyl-oxygen bond to the Rh center. The N-acyl carbonyl oxygen is bound to the Rh in these initial adducts, but is displaced upon addition of PMe3. Remarkably, both initial products and their PMe3 adducts are formed as single five-coordinate diastereomers in essentially quantitative yields. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00311-3

文献信息

• Tuning of the Structures of Chiral Phosphane-Phosphites: Application to the Highly Enantioselective Synthesis of α-Acyloxy Phosphonates by Catalytic Hydrogenation
  作者：Miguel Rubio、Sergio Vargas、Andrés Suárez、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1002/chem.200601032

  日期：2007.2.12

  ligands 1 and 5 in catalytic asymmetric hydrogenations of enol phosphonates 12 demonstrated a critical influence of the steric characteristics of the phosphane-phosphite in the course of the reaction, and optimization of the two phosphorus functionalities resulted in the production of versatile and efficient catalysts for this class of hydrogenations: enantioselectivities of up to 98% ee were thus obtained

  已经制备了一系列新的手性膦-亚磷酸酯5，并用于合成[Rh（cod）（5）] BF4（7）的铑配合物。在制备7中使用大的膦或亚磷酸酯基团避免了不希望的二取代的配合物的形成，其中一种已经被分离和表征了（9a）。配体5显示出与较大的膦亚磷酸酯1的重要区别：配合物7-不同于其刚性的[Rh（cod）（1）] 对应物-在溶液中显示了通量行为，与配位平面周围的骨架振动一致。在烯醇膦酸酯12的催化不对称氢化中对配体1和5的详细筛选表明，在反应过程中，膦亚磷酸酯的空间特征具有关键影响，两种磷官能团的优化以及对这类氢化反应的通用催化剂的生产：利用在β位带有烷基取代基的底物获得了高达98％ee的对映选择性，而对于具有挑战性的芳基对应物ee值高达92％。还研究了膦酸酯12a对Rh膦-亚磷酸酯片段的配位模式，并且观察到烯烃片段优先占据亚磷酸酯基团的顺式位置。从该观察结果也可以解释氢化膦酸酯的构型。因此，对于在
• Asymmetric hydrogenation of imines catalyzed by iridium complexes with phosphine–phosphite ligands: importance of backbone flexibility
  作者：Sergio Vargas、Miguel Rubio、Andrés Suárez、Antonio Pizzano

  DOI：10.1016/j.tetlet.2005.01.144

  日期：2005.3

  Chiral phosphine–phosphites provide an alternative class of ligands for the iridium catalyzed enantioselective hydrogenation of imines. Optimization of ligand structure has afforded enantioselectivities up to 84% ee in the reduction of N-aryl imines. A significant influence of backbone nature on enantioselectivity has also been observed.

  手性膦-亚磷酸酯为铱催化的亚胺对映选择性氢化提供了另一类配体。配体结构的优化在N-芳基亚胺的还原中提供了高达84％ee的对映选择性。还已经观察到主链性质对对映选择性的显着影响。