R(+)-o'-(1,1'-binaphthyl-2,2'-diyl)bis(diphenylphosphane)palladium(II) bis(triflate) | 358978-95-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: R(+)-o'-(1,1'-binaphthyl-2,2'-diyl)bis(diphenylphosphane)palladium(II) bis(triflate)
• 英文别名: [(2,2'-bis(diphenylphosphino)-1,1'-binaphtyl)Pd(OSO2CF3)2]；cis-Pd(R(+)-BINAP)(OTf)2；Pd(II)(2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl)(TfO)2；[1-(2-Diphenylphosphanylnaphthalen-1-yl)naphthalen-2-yl]-diphenylphosphane;palladium(2+);trifluoromethanesulfonate
• CAS: 358978-95-7；320635-27-6；177427-91-7；181658-30-0
• 化学式: C₄₆H₃₂F₆O₆P₂PdS₂
• 分子量: 1027.25
• InChiKey: IKTDILIXDHCGSB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.28
• 重原子数：
  63
• 可旋转键数：
  7
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  R(+)-o'-(1,1'-binaphthyl-2,2'-diyl)bis(diphenylphosphane)palladium(II) bis(triflate) 、 135-三(吡啶-4-乙炔基)苯 以 二氯甲烷 为溶剂， 以89%的产率得到
  参考文献：
  名称：

  Transition-Metal-Mediated Rational Design and Self-Assembly of Chiral, Nanoscale Supramolecular Polyhedra with Unique T Symmetry

  摘要：

  A novel family of chiral, discrete, nanoscale-sized supramolecular cages are prepared, via self-assembly and noncovalent interactions from the tridentate ligand 1,3,5-tris[(4-pyridyl)ethynyl]benzene and [(R)-(+)-BINAP]Pd-II and -Pt-II bis(triflates). The cationic parts of these highly symmetrical species possess large three-dimensional cavities and are rare examples of molecules with T symmetry.

  DOI：

  10.1021/om9702993
• 作为产物：
  描述：

  二氯[2，2’-二(二苯基磷)-1，1’-联萘]钯(II) 、 silver trifluoromethanesulfonate 以 not given 为溶剂， 生成 R(+)-o'-(1,1'-binaphthyl-2,2'-diyl)bis(diphenylphosphane)palladium(II) bis(triflate)
  参考文献：
  名称：

  钯（II）和铂（II）的阳离子配合物，作为路易斯酸催化剂，用于Diels-Alder反应

  摘要：

  一系列的Pd（II）和Pt（II）的种类的阳离子络合物的合成[（P-P）M（SOLV）]（Y）2，[（P-P）M（η 2 -Y）] （Y），和[（P-P）M（μ-Cl）的] 2（Y）2（其中，P-P =各种二膦包括手性二膦（M =钯，铂; Y = TFO -，CLO 4 - ，BF 4 -）被报告。所有的配合物都是环戊二烯或环己二烯与许多简单的双亲物如丙烯醛，甲基丙烯醛和甲基乙烯基酮之间的狄尔斯-阿尔德反应的极佳催化剂。在温和的条件下，在中等ee的条件下，手性二膦酸酯修饰的某些配合物可在Diels-Alder反应中充当对映选择性催化剂。在这方面的关键点是催化剂中仅存在一个空的配位点。

  DOI：

  10.1021/om0003943
• 作为试剂：
  描述：

  1-烯丙基-4-甲基苯 、 3,3,3-三氟丙酮酸乙酯 在 R(+)-o'-(1,1'-binaphthyl-2,2'-diyl)bis(diphenylphosphane)palladium(II) bis(triflate) 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以93%的产率得到ethyl (R,E)-2-(trifluoromethyl)-2-hydroxy-5-p-tolylpent-4-enoate
  参考文献：
  名称：

  Asymmetric carbonyl-ene and Friedel–Crafts reactions catalysed by Lewis acid platinum group metal complexes of the enantiopure atropisomeric biaryl-like diphosphine (S)-Me2-CATPHOS: a comparison with BINAP

  摘要：

  Lewis acid platinum and palladium complexes of (S)-Me-2-CATPHOS catalyse the carbonyl-ene reaction between allylbenzene derivatives and ethyl trifluoropyruvate to give the expected alpha-hydroxy esters with ee's up to 97%, while the corresponding reaction involving 2-allylfuran and thiophene was exclusively selective for Friedel-Crafts-type reactivity and gave the corresponding 2-hydroxy-trifluoromethyl ethyl esters in good yield and moderate to good enantioselectivity. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.022

文献信息

• Self-Assembly, Chiroptical Properties, and Host−Guest Chemistry of Chiral Pt−Pt and Pt−Pd Tetranuclear Macrocycles. Circular Dichroism Studies on Neutral Guest Inclusion Phenomena
  作者：Christian Müller、Jeffery A. Whiteford、Peter J. Stang

  DOI：10.1021/ja9820801

  日期：1998.9.1

  of cyclic, chiral molecular squares in 84−99% yields via self-assembly. CD studies and optical rotation of the chiral macrocycles and their corresponding precursors reveal that the chiroptical properties are mainly determined by the BINAP moiety. The host−guest chemistry of the chiral 4-ethynylpyridine tetramers with silver triflate and the capture of neutral guests via the resulting square Lewis acid/base

  描述了光学活性混合、带中性电荷的 Pt/Pt 和 Pt/Pd 大环配合物的合成、表征和圆二色 (CD) 光谱，以及它们相应前体的 CD 光谱。顺式-Pt(DIOP)(4-乙炔基吡啶)2 的手性单体（R(-)-DIOP 或 S(+)-DIOP）与手性双三氟甲磺酸酯（R(+)-BINAP 或 S(-)）之间的相互作用BINAP)) Pt(II) 或 Pd(II) 双膦或顺式 Pd(PEt3)2(OSO2CF3)2，在室温下的 CH2Cl2 中形成环状手性分子正方形，产率 84-99%。集会。手性大环及其相应前体的 CD 研究和旋光度表明，手性光学性质主要由 BINAP 部分决定。
• Directed Self-Assembly of Chiral, Optically Active Macrocyclic Tetranuclear Molecular Squares
  作者：Peter J. Stang、Bogdan Olenyuk

  DOI：10.1002/anie.199607321

  日期：1996.4.19
• Self-Assembly of Porphyrin Arrays via Coordination to Transition Metal Bisphosphine Complexes and the Unique Spectral Properties of the Product Metallacyclic Ensembles
  作者：Jun Fan、Jeffery A. Whiteford、Bogdan Olenyuk、Michael D. Levin、Peter J. Stang、Everly B. Fleischer

  DOI：10.1021/ja9839825

  日期：1999.3.1

  Self-assembly of predesigned angular and linear dipyridylporphyrin modules with bisphosphine-coordinated Pd(II) and Pt(II) angular and linear modules leads to cyclic porphyrin arrays containing two or four units and ranging in size from 15 to 39 Angstrom. Multinuclear NMR spectra indicate high symmetry for these macrocycles. Restriction in rotation of trans-DPyDPP groups around the axis defined by the terminal metal-nitrogen bonds distorts the symmetry of the tetramers, but the rotation is unrestricted at elevated temperatures. Chiral metal triflates containing R(+)- or S(-)-BINAP phosphines promote formation of enantiomeric macrocycles with a puckered geometry CD spectra of the chiral macrocycles reveal a strong exciton coupling between the porphyrin chromophores in the tetramers. Emission spectra reveal moderate fluorescence quenching of the dipyridylporphyrin fluorophores upon treatment with metal triflates and concomitant incorporation into the macrocycles.
• Cationic Complexes of Palladium(II) and Platinum(II) as Lewis Acid Catalysts for the Diels−Alder Reaction
  作者：Kristian Pignat、Jacopo Vallotto、Francesco Pinna、Giorgio Strukul

  DOI：10.1021/om0003943

  日期：2000.11.1

  The synthesis of a series of Pd(II) and Pt(II) cationic complexes of the types [(P−P)M(solv)](Y)2, [(P−P)M(η2-Y)](Y), and [(P−P)M(μ-Cl)]2(Y)2 (where P−P = various diphosphines including chiral diphosphines (M = Pd, Pt; Y = TfO-, ClO4-, BF4-) is reported. All complexes are excellent catalysts for the Diels−Alder reaction between cyclopentadiene or cyclohexadiene and a number of simple dienophiles such

  一系列的Pd（II）和Pt（II）的种类的阳离子络合物的合成[（P-P）M（SOLV）]（Y）2，[（P-P）M（η 2 -Y）] （Y），和[（P-P）M（μ-Cl）的] 2（Y）2（其中，P-P =各种二膦包括手性二膦（M =钯，铂; Y = TFO -，CLO 4 - ，BF 4 -）被报告。所有的配合物都是环戊二烯或环己二烯与许多简单的双亲物如丙烯醛，甲基丙烯醛和甲基乙烯基酮之间的狄尔斯-阿尔德反应的极佳催化剂。在温和的条件下，在中等ee的条件下，手性二膦酸酯修饰的某些配合物可在Diels-Alder反应中充当对映选择性催化剂。在这方面的关键点是催化剂中仅存在一个空的配位点。
• Transition-Metal-Mediated Rational Design and Self-Assembly of Chiral, Nanoscale Supramolecular Polyhedra with Unique <i>T</i> Symmetry
  作者：Peter J. Stang、Bogdan Olenyuk、David C. Muddiman、Richard D. Smith

  DOI：10.1021/om9702993

  日期：1997.7.1

  A novel family of chiral, discrete, nanoscale-sized supramolecular cages are prepared, via self-assembly and noncovalent interactions from the tridentate ligand 1,3,5-tris[(4-pyridyl)ethynyl]benzene and [(R)-(+)-BINAP]Pd-II and -Pt-II bis(triflates). The cationic parts of these highly symmetrical species possess large three-dimensional cavities and are rare examples of molecules with T symmetry.