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An Enantioselective Oxidative C-H/C-H Cross-Coupling Reaction: Highly Efficient Method to Prepare Planar Chiral Ferrocenes

A Pd-catalyzed, asymmetric oxidative cross-coupling reaction between ferrocenes and heteroarenes is described. The process, which takes place via a twofold C-H bond activation pathway, proceeds with modest to high efficiencies (36-86%) and high levels of regio- and enantioselectivity (95-99% ee). In the reaction, air oxygen serves as a green oxidant and excess amounts of the coupling partners are not required. The process is the first example of a catalytic asymmetric biaryl coupling reaction that occurs via double C-H bond activation. Finally, the generated coupling products can be readily transformed into chiral ligands and catalysts.

An Enantioselective Oxidative C-H/C-H Cross-Coupling Reaction: Highly Efficient Method to Prepare Planar Chiral Ferrocenes

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Host-Guest-Induced Electron Transfer Triggers Radical-Cation Catalysis

Modifying the reactivity of substrates by encapsulation is a fundamental principle of capsule catalysis. Here we show an alternative strategy, wherein catalytic activation of otherwise inactive quinone “co-factors” by a simple Pd2L4 capsule promotes a range of bulk-phase, radical-cation cycloadditions. Solution electron-transfer experiments and cyclic voltammetry show that the cage anodically shifts the redox potential of the encapsulated quinone by a significant 1 V. Moreover, the capsule also protects the reduced semiquinone from protonation, thus transforming the role of quinones from stoichiometric oxidants into catalytic single-electron acceptors. We envisage that the host-guest-induced release of an “electron hole” will translate to various forms of non-encapsulated catalysis that involve other difficult-to-handle, highly reactive species.

Host-Guest-Induced Electron Transfer Triggers Radical-Cation Catalysis

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Synthesis, coordination chemistry, and catalytic application of a novel unsymmetrical P/O ferrocenediyl ligand

A novel, unsymmetrical 1,1?-disubstituted ferrocenediyl ligand, 1-(diphenylphosphino)-1?-(methoxy)ferrocene (3), featuring phosphine and ether substituents has been synthesized via two different routes and structurally characterized. Its coordination chemistry was investigated by reaction with Rh(I), Cu(I), and group 10 metal precursors. With Ni(II) precursors, chelating complexes are formed in high yield, whereas with Pd(II) and Pt(II) precursors, either chelating complexes or monodentate bis ligand complexes with trans phosphorus ligation may be formed depending on the reaction conditions and metal precursor employed. A similar monodentate trans phosphorus-ligated complex is observed with Rh(I), whereas with Cu(I) precursors, a phosphorus-ligated monodentate bis ligand complex with a coordinated acetonitrile was obtained. Preliminary studies show that 3, in combination with either Pd(II) or Pd(0) precursors, can act as a catalyst for the Suzuki coupling reaction.

Synthesis, coordination chemistry, and catalytic application of a novel unsymmetrical P/O ferrocenediyl ligand

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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PROCESS FOR THE MANUFACTURE OF SUBSTITUTED PROPIONIC ACIDS

The invention concerns a process for the manufacture of substituted propionic acids comprising providing a substrate of formula (I): And subjecting the substrate to enantioselective hydrogenation under enantioselective hydrogenation conditions in the presence of an enantioselective hydrogenation catalyst comprising a catalyst ligand having a metallocene group with a chiral phosphorus or arsenic substituent to provide in enantiomeric excess a product of formula (II): or its enantiomer or if applicable its diastereomer.

PROCESS FOR THE MANUFACTURE OF SUBSTITUTED PROPIONIC ACIDS

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Photocatalytic oxidation of iron(II) complexes by dioxygen using 9-mesityl-10-methylacridinium ions

Photocatalytic oxidation of iron(ii) complexes by dioxygen occurred using the organic photocatalysts, 9-mesityl-10-methylacridinium ions (Acr+-Mes) and 2-phenyl-4-(1-naphthyl) quinolinium ions (QuPh+-NA), in the presence of triflic acid in acetonitrile under visible light irradiation. The electron-transfer state of Acr+-Mes produced upon photoexcitation oxidized the iron(ii) complexes, whereas it reduced dioxygen with protons to produce iron(iii) complexes and H2O2.

Photocatalytic oxidation of iron(II) complexes by dioxygen using 9-mesityl-10-methylacridinium ions

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Indirectly connected bis(N-Heterocyclic Carbene) bimetallic complexes: Dependence of metal-metal electronic coupling on linker geometry

Reaction of l,l’,3,3′-tetra(tert-amyl)benzobis(imidazolylidene) (1) with 2 equiv of FcN3 or FcNCS afforded bisadducts [(FcN3) 2(1)] (2) or [(FcNCS)2(1)] (3), respectively (Fc = ferrocene). To the best of our knowledge, these represent the first examples of complexes comprising metals indirectly connected to the carbene atoms of N-heterocyclic carbenes (NHCs) via their ligand sets. Cyclic and differential pulse voltammetry indicated that bis(NHC) 1 facilitated significant electronic coupling between ferrocene centers in 2 (DeltaE = 140 mV), but not in 3. We believe the different degrees of electronic interaction are due to geometric factors: the triazene linker in 2 is nearly coplanar with the bis(NHC) scaffold, whereas the isothiocyanate linker is orthogonal, as determined by X-ray crystallography. Employing this “indirect connection” strategy should enable tuning of metalmetal interactions by simple alteration the organic linker between NHC and MLn fragments rather than complete redesign thereof. Given that NHC-reactive azide or isothiocyanate groups can be incorporated into both organic and inorganic compounds, this approach is envisioned to facilitate access to otherwise inaccessible catalysts and materials.

Indirectly connected bis(N-Heterocyclic Carbene) bimetallic complexes: Dependence of metal-metal electronic coupling on linker geometry

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Reorganization energies of diprotonated and saddle-distorted porphyrins in photoinduced electron-transfer reduction controlled by conformationaldistortion

Kinetics of photoinduced electron transfer from a series of electron donors to the triplet excited states of a series of nonplanar porphyrins, hydrochloride salts of saddle-distorted dodecaphenylporphyrin ([H 4 DPP]Cl 2 ), tetrakis(2,4,6-trimethylphyenyl)porphyrin ([H 4 TMP]Cl 2 ), tetraphenylporphyrin ([H 4 TPP]Cl 2 ), and octaphenylporphyrin ([H 4 OPP]Cl 2), were investigated in comparison with those of a planar porphyrin, zinc [tetrakis(pentafluorophenyl)]porphyrin [Zn(F 20 TPP)(CH 3 CN)], in deaerated acetonitrile by laser flash photolysis. Theresulting data were evaluated in light of the Marcus theory of electron transfer, allowing us to determine reorganization energies of electron transfer to be 1.21 eV for [H 4 TMP]Cl 2 ,1.29 eV for [H 4 TPP]Cl 2 , 1.45 eV for [H 4 OPP]Cl 2 , 1.69 eV for [H 4 DPP]Cl 2 , and 0.84 eV for [Zn(F 20 TPP)(CH 3 CN)]. The reorganization energies exhibited a linear correlation relative to the out-of-plane displacements, which represent the degree of nonplanarity. The rate of electron-transfer reduction of diprotonated porphyrins is significantly slowed down byconformational distortions of the porphyrin ring. This indicates that t he reorganization energy of electron transfer is governed by structural change, giving a larger contribution of inner-sphere bond reorganizationenergy rather than outer-sphere solvent reorganization energy.

Reorganization energies of diprotonated and saddle-distorted porphyrins in photoinduced electron-transfer reduction controlled by conformationaldistortion

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Oxidative purification of halogenated ferrocenes

We report the large scale syntheses and ‘oxidative purification’ of fcI2, fcBr2 and FcBr (fc = ferrocene-1,1?-diyl, Fc = ferrocenyl). These valuable starting materials are typically laborious to separate via conventional techniques, but can be readily isolated by taking advantage of their increased E1/2 relative to FcH/FcX contaminants. Our work extends this methodology towards a generic tool for the separation of redox active mixtures.

Oxidative purification of halogenated ferrocenes

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ruthenium complexes with dendritic ferrocenyl phosphanes: Synthesis, characterization, and application in the catalytic redox isomerization of allylic alcohols

An efficient system for the catalytic redox isomerization of the allylic alcohol 1-octen-3-ol to 3-octanone is presented. The homogeneous ruthenium(II) catalyst contains a monodentate phosphane ligand with a ferrocene moiety in the backbone and provides 3-octanone in quantitative yields. The activity is increased by nearly 90 % with respect to the corresponding triphenyl phosphane ruthenium(II) complex. By grafting the catalyst at the surface of a dendrimer, the catalytic activity is further increased. By introducing different spacers between ferrocene and phosphorus, the influence on the electronic properties of the complexes is shown by evaluating the electrochemical behavior of the compounds.

Ruthenium complexes with dendritic ferrocenyl phosphanes: Synthesis, characterization, and application in the catalytic redox isomerization of allylic alcohols

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Various metalloligands and inorganic-organic hybrid bridging ligands have been incorporated in polynuclear complexes and bimetallic coordination polymers. Ferrocene, exhibiting redox activity and facile chemical modification, is a versatile metalloligand component. However, most metal complexes with ferrocene-containing ligands form discrete low-dimensional chelate complexes or coordination polymers. Thus, we designed and synthesized ferrocene-based multidentate ligands, 1,2-di(4-pyridylthio)ferrocene (L1) and 1,2-di(2-pyridylthio)ferrocene (L2). Here we report the synthesis and structures of molecular square complexes and coordination polymers containing L1, which reacted with M(hfac)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) and AgCF3SO3 to yield molecular square complexes [M(hfac)2(L1)]2¡¤2C6H5CH3 [M = Ni (1) and Co (2)] and [Ag(CF3SO3)(L1)(H2O)0.5]2¡¤2CH2Cl2¡¤H2O (3). The molecular square units comprise two metal ions bridged by two ligands. Isomorphic complexes 1 and 2 accommodate two toluene molecules above and below the molecular square. L1 reacted with Cu(hfac)2 and CuI to yield zigzag, {[Cu(hfac)2(L1)]}n¡¤0.25n(CH2Cl2) (4), and ribbon-shaped, {[Cu4I4(L1)2]}n (5), coordination polymers. In 4, L1 behaves as a bidentate N,N-ligand bridging the CuII ions, while in 5 it acts as a tridentate S,N,N-ligand linking the stepped-cubane Cu4I4 units. L1 reacted with AgX to form two-dimensional coordination polymers {[Ag(ClO4)(L1)]}n (6) and {[Ag(L1)]PF6}n (7), in which it acted as a tetradentate S,S,N,N-ligand. These complexes have topologies based on multidentate coordination of 1,2-substituted L1.

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion