(S)-4-[(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-4-[(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalene
• 英文别名: 1-diphenylphosphino-1-{(S)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yloxy}methane；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(diphenyl)phosphane
• 化学式: C₃₃H₂₄O₃P₂
• 分子量: 530.499
• InChiKey: HGFDPAPVPIUXKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-4-[(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalene 在 selenium 作用下， 以 苯 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  Phosphine–phosphite ligands: chelate ring size vs. activity and enantioselectivity relationships in asymmetric hydrogenation

  摘要：

  合成了一系列新型膦-亚磷酸酯配体P(C)nOP (n = 1-4)，并用于铑催化前手性烯烃的不对称氢化，以研究螯合环尺寸的影响。在衣康酸二甲酯的氢化中获得了优异的ee（高达97.5％），并且在（Z）-α-乙酰氨基肉桂酸甲酯的氢化中观察到随着配体主链长度的增加，活性和对映选择性增加。

  DOI：

  10.1039/c2dt30386h
• 作为产物：
  描述：

  (R)-(1,1′-联萘-2,2′-二氧)氯膦 、 (二苯基膦基)甲醇 在 三乙胺 作用下， 以 甲苯 为溶剂， 以85%的产率得到(S)-4-[(diphenylphosphanyl)methoxy]-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4a']dinaphptalene
  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

• Rhodium(I), Palladium(II), and Platinum(II) Complexes Containing New Mixed Phosphane−Phosphite Ligands − Effect of the Catalytic System Stability on the Enantioselective Hydroformylation of Styrene
  作者：Carmela G. Arena、Felice Faraone、Claudia Graiff、Antonio Tiripicchio

  DOI：10.1002/1099-0682(200203)2002:3<711::aid-ejic711>3.0.co;2-e

  日期：2002.3

  The new mixed phosphane−phosphite ligands 1 and 2, derived from 3,3′-di-tert-butyl-2,2′-dihydroxy-5,5′-dimethoxybiphenyl and (S)-binaphthol, respectively, reacted with [Rh(COD)(THF)2]CF3SO3 to give the compounds [Rh(COD)(1)]CF3SO3 and [Rh(COD)(2)]CF3SO3 in which the ligands 1 and (S)-2 are chelated to the rhodium centre. The reaction with [Rh(CO)2Cl]2 gave two different products, [Rh(CO)2(L)Cl] and

  新的混合膦-亚磷酸酯配体 1 和 2，分别衍生自 3,3'-二叔丁基-2,2'-二羟基-5,5'-二甲氧基联苯和 (S)-联萘酚，分别与 [Rh (COD)(THF)2]CF3SO3 得到化合物 [Rh(COD)(1)]CF3SO3 和 [Rh(COD)(2)]CF3SO3，其中配体 1 和 (S)-2 与铑螯合中心。与 [Rh(CO)2Cl]2 的反应得到两种不同的产物，[Rh(CO)2(L)Cl] 和 [Rh(CO)(L)Cl][L = 1 和 (S)-2]，含有 L 作为螯合物。根据 IR 和 NMR 光谱数据，五配位物质的拟议结构是三角双锥酰胺，其中磷烷-亚磷酸酯配体呈赤道轴配位。1和2与[Pd(C6H5CN)2Cl2]和[Pt(COD)I2]反应得到相应的化合物[Pd(L)Cl2]和[Pt(L)I2]，其中配体与金属螯合中心。[Pd(L)Cl2] 氯仿溶剂化物的晶体结构通过 X
• 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.
• Phosphine–phosphite ligands: chelate ring size vs. activity and enantioselectivity relationships in asymmetric hydrogenation
  作者：Gergely Farkas、Szabolcs Balogh、József Madarász、Áron Szöllősy、Ferenc Darvas、László Ürge、Maryse Gouygou、József Bakos

  DOI：10.1039/c2dt30386h

  日期：——

  A series of new phosphine–phosphite ligands P(C)nOP (n = 1–4) have been synthesized and used for rhodium-catalyzed asymmetric hydrogenation of prochiral olefins in order to study the effect of the chelate ring size. Excellent ees (up to 97.5%) were obtained in the hydrogenation of dimethyl itaconate and an increase of activity and enantioselectivity was observed in the hydrogenation of (Z)-α-acetamidocinnamic acid methyl ester with the increasing length of the backbone of the ligands.

  合成了一系列新型膦-亚磷酸酯配体P(C)nOP (n = 1-4)，并用于铑催化前手性烯烃的不对称氢化，以研究螯合环尺寸的影响。在衣康酸二甲酯的氢化中获得了优异的ee（高达97.5％），并且在（Z）-α-乙酰氨基肉桂酸甲酯的氢化中观察到随着配体主链长度的增加，活性和对映选择性增加。