diethyl (2R,5R)-[2-(2,5-dimethylpyrrolidin-1-yl)phenyl]phosphinite | 524931-59-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: diethyl (2R,5R)-[2-(2,5-dimethylpyrrolidin-1-yl)phenyl]phosphinite
• 英文别名: diethyl 2-[(2R,5R)-2,5-dimethylpyrrolidin-1-yl]phenylphosphonite；[2-[(2R,5R)-2,5-dimethylpyrrolidin-1-yl]phenyl]-diethoxyphosphane
• CAS: 524931-59-7
• 化学式: C₁₆H₂₆NO₂P
• 分子量: 295.362
• InChiKey: FAEXRBSWNKEYEU-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl (2R,5R)-[2-(2,5-dimethylpyrrolidin-1-yl)phenyl]phosphinite 在 lithium aluminium tetrahydride 、 三甲基氯硅烷 作用下， 以 四氢呋喃 为溶剂， 生成 (R,R)-1-{2-[(R,R)-2,4-dimethylpyrrolidino]phenyl}-2,5-dimethylphospholane borane complex
  参考文献：
  名称：

  Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium-Catalyzed Allylic Substitutions

  摘要：

  Chiral P,N-ligands with pseudo-C-2 and pseudo-C-s symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C-2-symmetric ligands based on the binaphthyl skeleton than with the analogous C-2-symmetric P,P- and N,N-analogues. Pseudo-C-2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.

  DOI：

  10.1021/jo026889e
• 作为产物：
  描述：

  (4S,7S)-4,7-dimethyl-1,3,2-dioxathiepane 2,2-dioxide 在 三乙烯二胺 、 叔丁基锂 作用下， 以 乙醚 、 甲苯 、 正戊烷 为溶剂， 反应 115.0h， 生成 diethyl (2R,5R)-[2-(2,5-dimethylpyrrolidin-1-yl)phenyl]phosphinite
  参考文献：
  名称：

  Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium-Catalyzed Allylic Substitutions

  摘要：

  Chiral P,N-ligands with pseudo-C-2 and pseudo-C-s symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C-2-symmetric ligands based on the binaphthyl skeleton than with the analogous C-2-symmetric P,P- and N,N-analogues. Pseudo-C-2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.

  DOI：

  10.1021/jo026889e

文献信息

• Probing the Importance of the Hemilabile Site of Bis(phosphine) Monoxide Ligands in the Copper-Catalyzed Addition of Diethylzinc to <i>N</i>-Phosphinoylimines: Discovery of New Effective Chiral Ligands
  作者：Isabelle Bonnaventure、André B. Charette

  DOI：10.1021/jo800969x

  日期：2008.8.1

  hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding α-chiral amines were obtained in high yields (80−98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu•2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of β,β-disubstituted

  半不稳定的配体Me-DuPHOS（O）2已被证明是铜催化将二乙基锌加成到N-膦基嘧啶中的成功配体。以高收率（80-98％）和对映体比率（19.0：1至99.0：1 er）获得了相应的α-手性胺。此外，已经表明该Cu 2催化体系在将二乙基锌添加到硝基烯烃中和减少β，β-二取代的乙烯基苯基砜方面是有效的。本文描述了一般的结构/选择性研究，其中三个配体亚基（手性磷酰基-连接基-不稳定的配位基团（Z））被系统地修饰，并在铜催化的二乙基锌加到N-膦基嘧啶1中进行了测试。衍生自苯甲醛。这项研究导致发现了一类新的有效手性配体，其结合了一个手性磷烷单元和一个非手性氧化膦。
• Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium-Catalyzed Allylic Substitutions
  作者：Jean-Luc Vasse、Robert Stranne、Raivis Zalubovskis、Carole Gayet、Christina Moberg

  DOI：10.1021/jo026889e

  日期：2003.4.1

  Chiral P,N-ligands with pseudo-C-2 and pseudo-C-s symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C-2-symmetric ligands based on the binaphthyl skeleton than with the analogous C-2-symmetric P,P- and N,N-analogues. Pseudo-C-2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.