N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine
• 英文别名: N-benzyl-N-[[(2S)-1-(12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yl)pyrrolidin-2-yl]methyl]-12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-amine
• 化学式: C₅₂H₄₀N₂O₄P₂
• 分子量: 818.848
• InChiKey: XZXQFQMKDBXNEJ-FAIXQHPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14
• 重原子数：
  60
• 可旋转键数：
  6
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  59
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  bis(η3-allyl-μ-chloropalladium(II)) 、 N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine 、 silver tetrafluoroborate 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 3.0h， 以91%的产率得到[Pd(allyl)((S_a,S_a)-N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine)]BF4
  参考文献：
  名称：

  BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

  摘要：

  New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C-1 backbone symmetry have been prepared from (S-a)- and (R-a)-1,1'-binaphthy1-2,2'-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of a-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.06.019
• 作为产物：
  描述：

  (R)-(1,1′-联萘-2,2′-二氧)氯膦 、 (S)-2-(benzylaminomethyl)pyrrolidine 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 甲苯 为溶剂， 以83%的产率得到N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine
  参考文献：
  名称：

  BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

  摘要：

  New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C-1 backbone symmetry have been prepared from (S-a)- and (R-a)-1,1'-binaphthy1-2,2'-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of a-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.06.019
• 作为试剂：
  描述：

  衣康酸二甲酯 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 N-benzyl-N-(((2S)-1-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine 、 氢气 作用下， 以 2,2,2-三氟乙醇 为溶剂， 25.0 ℃ 、100.0 kPa 条件下， 反应 24.0h， 以94%的产率得到
  参考文献：
  名称：

  BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

  摘要：

  New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C-1 backbone symmetry have been prepared from (S-a)- and (R-a)-1,1'-binaphthy1-2,2'-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of a-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.06.019

文献信息

• BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis
  作者：Konstantin N. Gavrilov、Alexei A. Shiryaev、Ilya V. Chuchelkin、Sergey V. Zheglov、Eugenie A. Rastorguev、Vadim A. Davankov、Armin Börner

  DOI：10.1016/j.tetasy.2012.06.019

  日期：2012.7

  New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C-1 backbone symmetry have been prepared from (S-a)- and (R-a)-1,1'-binaphthy1-2,2'-diol (BINOL) and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of a-dehydrocarboxylic acid esters. The results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl moieties of the ligand and the nature of the solvent. (c) 2012 Elsevier Ltd. All rights reserved.