[2-(5,7-Dihydro-dibenzo[c,e]azepin-6-yl)-ethyl]-phosphonic acid diethyl ester | 524931-71-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: [2-(5,7-Dihydro-dibenzo[c,e]azepin-6-yl)-ethyl]-phosphonic acid diethyl ester
• 英文别名: 6-(2-Diethoxyphosphorylethyl)-5,7-dihydrobenzo[d][2]benzazepine
• CAS: 524931-71-3
• 化学式: C₂₀H₂₆NO₃P
• 分子量: 359.405
• InChiKey: DXISGVYOCGJGNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [2-(5,7-Dihydro-dibenzo[c,e]azepin-6-yl)-ethyl]-phosphonic acid diethyl ester 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以75%的产率得到6-(2-Phosphanyl-ethyl)-6,7-dihydro-5H-dibenzo[c,e]azepine
  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：

  diethyl (2-aminoethyl)phosphonate 、 2,2′-双(溴甲基)-1,1′-联苯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以93%的产率得到[2-(5,7-Dihydro-dibenzo[c,e]azepin-6-yl)-ethyl]-phosphonic acid diethyl ester
  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

• 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.