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-yloxymethyl)pyridine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 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-yloxymethyl)pyridine
• 英文别名: 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-yloxymethyl)pyridine
• 化学式: C₂₆H₁₈NO₃P
• 分子量: 423.408
• InChiKey: AFMOENPGTGHCPW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  48.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 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-yloxymethyl)pyridine 以 二氯甲烷 为溶剂， 反应 2.5h， 以85%的产率得到
  参考文献：
  名称：

  Rhodium-catalyzed asymmetric olefin hydrogenation by easily accessible aniline- and pyridine-derived chiral phosphites

  摘要：

  An aniline- and two pyridine-derived (R)-BINOL-based P,N-containing phosphite ligands have been synthesized via a one-pot procedure. Treatment of the aniline-derived ligand with 1 equiv of [Rh(COD)(2)]BF4 yielded a mixture of a P,N-chelate complex and a biligated P-monodentate complex (exclusively obtained by treatment of the ligand with rhodium in a ratio of 2:1), while the pyridine analogues led to the corresponding P,N-bidentate complexes as unique species. For the first time, such phosphites were studied for rhodium-catalyzed enantioselective olefin hydrogenation. At room temperature, the aniline-derived ligand was found to be more active and selective compared to the pyridine analogues, which can probably be attributed to its different coordination mode and the formation of a biligated P-monodentate complex. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.11.023
• 作为产物：
  描述：

  2-吡啶甲醇 、 (R)-(1,1′-联萘-2,2′-二氧)氯膦 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以86%的产率得到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-yloxymethyl)pyridine
  参考文献：
  名称：

  Rhodium-catalyzed asymmetric olefin hydrogenation by easily accessible aniline- and pyridine-derived chiral phosphites

  摘要：

  An aniline- and two pyridine-derived (R)-BINOL-based P,N-containing phosphite ligands have been synthesized via a one-pot procedure. Treatment of the aniline-derived ligand with 1 equiv of [Rh(COD)(2)]BF4 yielded a mixture of a P,N-chelate complex and a biligated P-monodentate complex (exclusively obtained by treatment of the ligand with rhodium in a ratio of 2:1), while the pyridine analogues led to the corresponding P,N-bidentate complexes as unique species. For the first time, such phosphites were studied for rhodium-catalyzed enantioselective olefin hydrogenation. At room temperature, the aniline-derived ligand was found to be more active and selective compared to the pyridine analogues, which can probably be attributed to its different coordination mode and the formation of a biligated P-monodentate complex. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.11.023

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.
• Rhodium-catalyzed asymmetric olefin hydrogenation by easily accessible aniline- and pyridine-derived chiral phosphites
  作者：Kalliopi A. Vallianatou、Dominik J. Frank、Georgia Antonopoulou、Spyros Georgakopoulos、Eleni Siapi、Maria Zervou、Ioannis D. Kostas

  DOI：10.1016/j.tetlet.2012.11.023

  日期：2013.1

  An aniline- and two pyridine-derived (R)-BINOL-based P,N-containing phosphite ligands have been synthesized via a one-pot procedure. Treatment of the aniline-derived ligand with 1 equiv of [Rh(COD)(2)]BF4 yielded a mixture of a P,N-chelate complex and a biligated P-monodentate complex (exclusively obtained by treatment of the ligand with rhodium in a ratio of 2:1), while the pyridine analogues led to the corresponding P,N-bidentate complexes as unique species. For the first time, such phosphites were studied for rhodium-catalyzed enantioselective olefin hydrogenation. At room temperature, the aniline-derived ligand was found to be more active and selective compared to the pyridine analogues, which can probably be attributed to its different coordination mode and the formation of a biligated P-monodentate complex. (C) 2012 Elsevier Ltd. All rights reserved.