Silver;13-oxido-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: Silver;13-oxido-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide
• 英文别名: silver;13-oxido-12,14-dioxa-13λ5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide
• 化学式: Ag*C₂₀H₁₂O₄P
• 分子量: 455.155
• InChiKey: IFDUWGHUQZMLSX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  58.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  yttrium(III) chloride 、 Silver;13-oxido-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide 以 四氢呋喃 、 水 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates: Enantioselective Three-Component Asymmetric Aza-Diels–Alder Reactions of Cyclic Ketones

  摘要：

  A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P](3)) in solution. H-1 and P-31 NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)(III)/Y[P](3) complexes with bridging binaphthyl phosphate ligands. The Lewis acidity of these chiral bimetallic catalysts is readily tuned by changing either the metal Lewis acid or the chiral metal phosphate. Through cooperative metal Lewis acid-enamine catalysis, asymmetric three-component aza-Diels-Alder reactions of 5-, 6-, and 7-membered cyclic ketones, unsaturated ketoesters, and arylamines were successfully achieved to afford fused bicyclic dihydropyridines in high yields (up to 94%) with high enantioselectivity (up to 99% enantiomeric excess) and excellent chemoselectivity.

  DOI：

  10.1021/acs.joc.5b00895
• 作为产物：
  描述：

  silver carbonate 、 (R)-1,1'-binaphthyl-2,2'-phosphoric acid 以 二氯甲烷 、 水 为溶剂， 反应 2.0h， 以88%的产率得到Silver;13-oxido-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide
  参考文献：
  名称：

  银催化的不对称加成的O ？氢和氮？H键与烯键：基于非共价相互作用的立体选择性的新模型。

  摘要：

  银络合物的催化对映选择性加成的O-能力氢和氮 H键以丙二烯通过使用从oxophosphorus（V）中所取得的光学活性的阴离子配体酸作为手性的来源证明首次。最多可以将73％ee的酸，醇和胺分子内添加到艾伦烯中。利用CH端基异构作用，可以实现低ee的2取代四氢呋喃样品的绝对构型通过比较手部ORD和VCD测量值与计算得出的光谱，可以明确分配。在工作的第二部分，通过过渡态的DFT自由能计算来探究立体选择性的起源。基于非共价相互作用，开发了一种新的对映异构分化模型。该模型使我们能够将立体选择性的来源识别为弱的有吸引力的相互作用。这种分散力在不对称催化中常常被忽略。开发了一种新的计算方法，将这些相互作用表示为以彩色编码的等值面，其特征是降低了密度梯度分布。

  DOI：

  10.1002/chem.201200547
• 作为试剂：
  描述：

  benzyl 2-oxo-4-phenylbut-3-enoate 、 甲氧苯胺 、 环戊酮 在 yttrium(III) chloride 、 Silver;13-oxido-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene 13-oxide 作用下， 以 甲苯 为溶剂， 反应 12.0h， 生成 C₂₉H₂₇NO₃ 、 C₂₉H₂₇NO₃
  参考文献：
  名称：

  Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates: Enantioselective Three-Component Asymmetric Aza-Diels–Alder Reactions of Cyclic Ketones

  摘要：

  A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P](3)) in solution. H-1 and P-31 NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)(III)/Y[P](3) complexes with bridging binaphthyl phosphate ligands. The Lewis acidity of these chiral bimetallic catalysts is readily tuned by changing either the metal Lewis acid or the chiral metal phosphate. Through cooperative metal Lewis acid-enamine catalysis, asymmetric three-component aza-Diels-Alder reactions of 5-, 6-, and 7-membered cyclic ketones, unsaturated ketoesters, and arylamines were successfully achieved to afford fused bicyclic dihydropyridines in high yields (up to 94%) with high enantioselectivity (up to 99% enantiomeric excess) and excellent chemoselectivity.

  DOI：

  10.1021/acs.joc.5b00895

文献信息

• Late-Stage Diversification of Chiral N-Heterocyclic-Carbene Precatalysts for Enantioselective Homoenolate Additions
  作者：Pinguan Zheng、Chenaimwoyo A. Gondo、Jeffrey W. Bode

  DOI：10.1002/asia.201000617

  日期：2011.2.1

  A library of chiral triazolium salts has been prepared by late‐state diversification of a triazolium amine salt. By utilizing a primary amine as a functional handle, a single triazolium salt can be transformed into a variety of chiral N‐heterocyclic carbene precatalysts. This approach makes the preparation of chiral N‐heterocyclic carbenes possible by a single‐step modification of a triazolium salt

  通过三唑胺盐的后期多样化制备了手性三唑盐库。通过利用伯胺作为功能手柄，单一的三唑盐可以转化为多种手性N-杂环卡宾预催化剂。这种方法使得通过三唑鎓盐的一步修饰来制备手性N-杂环卡宾成为可能，而不是通常需要多步有机合成和为催化剂库的每个成员形成具有挑战性的杂环。我们筛选了这些催化剂，用于控制 α,β-不饱和醛和环状酮亚胺之间的 γ-内酰胺形成反应中的非对映选择性和对映选择性。
• Gold(I) Complexes of Conformationally Constricted Chiral Ferrocenyl Phosphines
  作者：Elena M. Barreiro、Diego F. D. Broggini、Luis A. Adrio、Andrew J. P. White、Rino Schwenk、Antonio Togni、King Kuok (Mimi) Hii

  DOI：10.1021/om300222k

  日期：2012.5.14

  The preparation of two new chiral, enantiopure, and conformationally constrained phosphocin and 1,5-diphosphocin, incorporating two ferrocenyl units, is described. The gold(I) chloride complexes of these ligands and (S)-(R)-PPF-OMe were prepared, and their structures, in solution and solid states, are compared. Abstraction of the chloride anion by the addition of silver salt of either toluenesulfonate or chiral BINOL-phosphates generates active catalysts for the intramolecular cyclization of 6-methyl-1,1-diphenylhepta-4,5-dien-1-ol, where up to 47% ee can be obtained. Match and mismatch effects between chiral ligands and counteranions are highlighted.
• Facile Synthesis of Effcient and Selective Ruthenium Olefin Metathesis Catalysts with Sulfonate and Phosphate Ligands
  作者：Peili Teo、Robert H. Grubbs

  DOI：10.1021/om1007924

  日期：2010.11.22

  A series of novel, air-stable ruthenium NHC catalysts with sulfonate and phosphate anions have been prepared easily in one pot at high yields using commercially available precursors. The catalysts were found to be effective for ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis. The catalysts showed higher cis-selectivity in olefin cross-metathesis reactions as compared to earlier known ruthenium-based olefin metathesis catalysts, with allylbenzene and cis-1,4-diacetoxybutene as substrates.
• Silver-Catalysed Enantioselective Addition of OH and NH Bonds to Allenes: A New Model for Stereoselectivity Based on Noncovalent Interactions
  作者：Jannine L. Arbour、Henry S. Rzepa、Julia Contreras-García、Luis A. Adrio、Elena M. Barreiro、King Kuok Mimi Hii

  DOI：10.1002/chem.201200547

  日期：2012.9.3

  complexes to catalyse the enantioselective addition of OH and NH bonds to allenes is demonstrated for the first time by using optically active anionic ligands that were derived from oxophosphorus(V) acids as the sources of chirality. The intramolecular addition of acids, alcohols, and amines to allenes can be achieved with up to 73 % ee. The exploitation of a CH anomeric effect allowed the absolute configuration

  银络合物的催化对映选择性加成的O-能力氢和氮 H键以丙二烯通过使用从oxophosphorus（V）中所取得的光学活性的阴离子配体酸作为手性的来源证明首次。最多可以将73％ee的酸，醇和胺分子内添加到艾伦烯中。利用CH端基异构作用，可以实现低ee的2取代四氢呋喃样品的绝对构型通过比较手部ORD和VCD测量值与计算得出的光谱，可以明确分配。在工作的第二部分，通过过渡态的DFT自由能计算来探究立体选择性的起源。基于非共价相互作用，开发了一种新的对映异构分化模型。该模型使我们能够将立体选择性的来源识别为弱的有吸引力的相互作用。这种分散力在不对称催化中常常被忽略。开发了一种新的计算方法，将这些相互作用表示为以彩色编码的等值面，其特征是降低了密度梯度分布。
• Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates: Enantioselective Three-Component Asymmetric Aza-Diels–Alder Reactions of Cyclic Ketones
  作者：Yongming Deng、Chamini V. Karunaratne、Erika Csatary、David L. Tierney、Kraig Wheeler、Hong Wang

  DOI：10.1021/acs.joc.5b00895

  日期：2015.8.21

  A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P](3)) in solution. H-1 and P-31 NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)(III)/Y[P](3) complexes with bridging binaphthyl phosphate ligands. The Lewis acidity of these chiral bimetallic catalysts is readily tuned by changing either the metal Lewis acid or the chiral metal phosphate. Through cooperative metal Lewis acid-enamine catalysis, asymmetric three-component aza-Diels-Alder reactions of 5-, 6-, and 7-membered cyclic ketones, unsaturated ketoesters, and arylamines were successfully achieved to afford fused bicyclic dihydropyridines in high yields (up to 94%) with high enantioselectivity (up to 99% enantiomeric excess) and excellent chemoselectivity.