(S)-2-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalen-4-yloxymethyl)pyridine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-2-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalen-4-yloxymethyl)pyridine
• 英文别名: (S)-(1,1'-binaphthyl-2,2'-yl) (2-pyridyl) phosphite；2-(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-yloxy)pyridine；2-(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-yloxy)pyridine
• 化学式: C₂₅H₁₆NO₃P
• 分子量: 409.381
• InChiKey: AHYFZAXZKLRCRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  48.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-羟基吡啶 、 (R)-(1,1′-联萘-2,2′-二氧)氯膦 在 三乙胺 作用下， 以 甲苯 为溶剂， 以35%的产率得到(S)-2-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalen-4-yloxymethyl)pyridine
  参考文献：
  名称：

  Structural control in palladium(II)-catalyzed enantioselective allylic alkylation by new chiral phosphine-phosphite and pyridine-phosphite ligands

  摘要：

  The ligands 6-[(diphenylphosphanyl)methoxy]-4,8-di-tert-butyl-2.10-dimethoxy-5,7-dioxa-6-phosphadibenzo[a,c]cycloheptene, 1, (S)-4-(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']-dinaphthalene, (S)-2, and (S)-4-(diphenylphosphanyl)methoxyl-2,6-bis-trimethylsilanyl-3,5-dioxa-4-phosphacyclohepta[2, cyclohepta[2,1-a;3,4-a']dinaphthalene, (S)-3, (S)-2-(3,5-dioxa-4-phosphacyclohepta[2, 1 -a;3,4-a']dinaphthalen-4-yl-oxymethyl)pyridine, (S)-4, and (S)-2-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphtalen-4-yl-oxy)pyridine, (S)-5, have been easily prepared.The cationic complexes [Pd(eta(3)-C3H5)(L-L')]CF3SO3 (L-L'=1-(S)-5) and [Pd(eta(3)-PhCHCHCHPh)-(L-L')]CF3SO3 (L-L' = (S)-2-(S)-4) were synthesized by conventional methods starting from the complexes [Pd(eta(3)-C3H5)Cl](2) and [Pd(eta(3)-PhCHCHCHPh)Cl](2), respectively. The behavior in solution of all the pi-allyl-and pi-phenylallyl-(L-L')palladium derivatives 6-14 was studied by H-1, P-31{H-1}, C-13{H-1} NMR and 2D-NOESY spectroscopy. As concerns the ligands (S)-4 and (S)-5, a satisfactory analysis of the structures in solution was possible only for palladium-allyl complexes [Pd(eta(3)-C3H5)(S)-4]CF3SO3, 11, and [Pd(eta(3)- C3H5)((S)-5)]CF3SO3, 12, since the corresponding species [Pd(eta(3)-PhCHCHCHPh)((S)-4)]CF3SO3, 13, and [Pd(eta(3)-PhCHCHCHPh)((S)-5)]CF3SO3, 14, revealed low stability in solution for a long time. The new ligands (S)-2-(S)-5 were tested in the palladium-catalyzed enantioselective substitution of (1,3-diphenyl-1,2-propenyl)acetate by dimethylmalonate. The precatalyst [Pd(eta(3)-C3H5)((S)-2)]CF3SO3 afforded the allyl substituted product in good yield (95%) and acceptable enantioselectivities (71% e.e. in the 5 form). A similar result was achieved with the precatalyst [Pd(eta(3)-C3H5)((S)-3)]CF3SO3. The nucleophilic attack of the malonate occurred preferentially at allylic carbon far from the binaphthalene moiety, namely tr ans to the phosphite group. When the complexes containing ligands (S)-4 and (S)-5 were used as precatalysts, the product was obtained as a racemic mixture in high yield. The number of the configurational isomers of the Pd-allyl intermediates present in solution in the allylic alkylation and the relative concentrations are considered a determining factor for the enantioselectivity of the process. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00227-5

文献信息

• Structural control in palladium(II)-catalyzed enantioselective allylic alkylation by new chiral phosphine-phosphite and pyridine-phosphite ligands
  作者：Carmela Grazia Arena、Dario Drommi、Felice Faraone

  DOI：10.1016/s0957-4166(00)00227-5

  日期：2000.7

  The ligands 6-[(diphenylphosphanyl)methoxy]-4,8-di-tert-butyl-2.10-dimethoxy-5,7-dioxa-6-phosphadibenzo[a,c]cycloheptene, 1, (S)-4-(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']-dinaphthalene, (S)-2, and (S)-4-(diphenylphosphanyl)methoxyl-2,6-bis-trimethylsilanyl-3,5-dioxa-4-phosphacyclohepta[2, cyclohepta[2,1-a;3,4-a']dinaphthalene, (S)-3, (S)-2-(3,5-dioxa-4-phosphacyclohepta[2, 1 -a;3,4-a']dinaphthalen-4-yl-oxymethyl)pyridine, (S)-4, and (S)-2-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphtalen-4-yl-oxy)pyridine, (S)-5, have been easily prepared.The cationic complexes [Pd(eta(3)-C3H5)(L-L')]CF3SO3 (L-L'=1-(S)-5) and [Pd(eta(3)-PhCHCHCHPh)-(L-L')]CF3SO3 (L-L' = (S)-2-(S)-4) were synthesized by conventional methods starting from the complexes [Pd(eta(3)-C3H5)Cl](2) and [Pd(eta(3)-PhCHCHCHPh)Cl](2), respectively. The behavior in solution of all the pi-allyl-and pi-phenylallyl-(L-L')palladium derivatives 6-14 was studied by H-1, P-31H-1}, C-13H-1} NMR and 2D-NOESY spectroscopy. As concerns the ligands (S)-4 and (S)-5, a satisfactory analysis of the structures in solution was possible only for palladium-allyl complexes [Pd(eta(3)-C3H5)(S)-4]CF3SO3, 11, and [Pd(eta(3)- C3H5)((S)-5)]CF3SO3, 12, since the corresponding species [Pd(eta(3)-PhCHCHCHPh)((S)-4)]CF3SO3, 13, and [Pd(eta(3)-PhCHCHCHPh)((S)-5)]CF3SO3, 14, revealed low stability in solution for a long time. The new ligands (S)-2-(S)-5 were tested in the palladium-catalyzed enantioselective substitution of (1,3-diphenyl-1,2-propenyl)acetate by dimethylmalonate. The precatalyst [Pd(eta(3)-C3H5)((S)-2)]CF3SO3 afforded the allyl substituted product in good yield (95%) and acceptable enantioselectivities (71% e.e. in the 5 form). A similar result was achieved with the precatalyst [Pd(eta(3)-C3H5)((S)-3)]CF3SO3. The nucleophilic attack of the malonate occurred preferentially at allylic carbon far from the binaphthalene moiety, namely tr ans to the phosphite group. When the complexes containing ligands (S)-4 and (S)-5 were used as precatalysts, the product was obtained as a racemic mixture in high yield. The number of the configurational isomers of the Pd-allyl intermediates present in solution in the allylic alkylation and the relative concentrations are considered a determining factor for the enantioselectivity of the process. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Screening of a Supramolecular Catalyst Library in the Search for Selective Catalysts for the Asymmetric Hydrogenation of a Difficult Enamide Substrate
  作者：Xiao-Bin Jiang、Laurent Lefort、P. Elsbeth Goudriaan、André H. M. de Vries、Piet W. N. M. van Leeuwen、Johannes G. de Vries、Joost N. H. Reek

  DOI：10.1002/anie.200503663

  日期：2006.2.13