Design of highly active heterogeneous palladium catalysts for the activation of aryl chlorides in Heck reactions

In situ generation of highly active palladium species by intermediate dissolution of Pd from solid supported catalysts has been demonstrated to be a very successful approach for the activation of aryl chlorides in Heck reactions. The new ‘heterogeneous’ Pd catalysts act as reservoir for molecular Pd species with unsaturated coordination sphere in solution. Crucial Pd leaching and re-deposition onto the support can be controlled by optimization of reaction conditions and by the properties of the catalysts. Pd is re-deposited onto the support at the end of the reaction. The catalysts, palladium supported on activated carbon, on various metal oxides or fluorides and Pd complexes in zeolites, are easy to prepare, though the preparation conditions are crucial. The catalysts convert all aryl bromides completely within minutes (TON 100,000). Aryl chlorides (even deactivated ones) are converted with high yields, within 2-6 h. The catalysts belong to the most active ones in Heck reactions at all (including best homogeneous systems) and fulfill all relevant requirements for practical applications in laboratory and industry.     

Oxidative Transformations of Organic Compounds Mediated by Redox Molecular Sieves

Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.^[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O₂, H₂O₂, and RO₂H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted.     

An expeditious preparation of E-2-amino-5-hydroxyadamantane and its Z-isomer

Reductive amination of 5-hydroxy-2-adamantanone with S-α-methylbenzylamine using 5% Rh-C as the catalyst in the presence of Al(iOPr)₃ gave a 3:1 mixture of the E- and Z-5-hydroxy-adamantane-1-phenethylamines. Choice of catalyst, concentration, solvent and the presence of the hydroxyl group on the adamantane influenced the stereoselectivity of the amination reaction. The desired E-isomer could be isolated by fractional crystallization from diisopropyl ether. Debenzylation gave the elusive E-2-amino-5-hydroxyadamantane in a 45% overall yield.     

Estimating reaction parameters in mechanism-enabled population balance models of nanoparticle size distributions: A Bayesian inverse problem approach

In order to quantitatively predict nano- as well as other particle-size distributions, one needs to have both a mathematical model and estimates of the parameters that appear in these models. Here, we show how one can use Bayesian inversion to obtain statistical estimates for the parameters that appear in recently derived mechanism-enabled population balance models (ME-PBM) of nanoparticle growth. The Bayesian approach addresses the question of “how well do we know our parameters, along with their uncertainties?.” The results reveal that Bayesian inversion statistical analysis on an example, prototype nanoparticle formation system allows one to estimate not just the most likely rate constants and other parameter values, but also their SDs, confidence intervals, and other statistical information. Moreover, knowing the reliability of the mechanistic model's parameters in turn helps inform one about the reliability of the proposed mechanism, as well as the reliability of its predictions. The paper can also be seen as a tutorial with the additional goal of achieving a “Gold Standard” Bayesian inversion ME-PBM benchmark that others can use as a control to check their own use of this methodology for other systems of interest throughout nature. Overall, the results provide strong support for the hypothesis that there is substantial value in using a Bayesian inversion methodology for parameter estimation in particle formation systems.     

Kinetic investigation of a PC(sp)P pincer palladium (II) complex in the Heck reaction

An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]-cyclohexane} palladium (II) iodide (1) has been performed in DMF-d₇ solution. Based on mercury poisoning experiments a heterogeneous palladium catalyst formed from the pre-catalyst is proposed. Saturation behaviour with respect to the olefin concentration suggests a mechanism consisting of a pre-equilibrium association of the olefin followed by a rate determining reaction with aryl halide. The equilibrium constant for the olefin association, K₁, and the rate constant for the subsequent oxidative addition step, k₂, were determined to (5.7 ± 2.5) × 10⁻³ and 18.4 ± 2.7 M⁻¹ s⁻¹, respectively.     

Surface and Subsurface Oxygen on Platinum in a Copper Perchlorate Solution

The formation of an adatom layer on polycrystalline platinum and the three-dimensional nucleation of copper in a copper perchlorate solution are studied by cyclic voltammetry at 0.1 V s^–1 while varying potential ranges and by recording potentiostatic current transients. About 0.6 monolayers of copper adatoms are deposited when cycling with anodic limit E _a = 1.35 V, the process is slower than that in an acid sulfate solution. Decreasing E _a accelerates the process (nearly one monolayer forms for E _a = 0.80–0.95 V in a cathodic scan) due to an increased number of active centers (metastable copper oxides) and, probably, to a change in the platinum surface microstructure. Oxygen for copper oxides is presumably supplied by water molecules adsorbed on a monolayer of copper adsorbed atoms and by subsurface oxygen (O_ss), which appears on the platinum surface after the destruction of complexes O_ss–Pt _n –ClO₄. Both the copper nucleation and the deposit growth accelerate at higher concentrations of copper oxides, which form at low E _a. High cathodic overvoltages decrease the number of active crystallization centers due to reduction or removal of copper oxides.     

Pillar[5]arene based conjugated macrocycle polymers with unique photocatalytic selectivity

The development of heterogeneous catalysts with substrate shape, size or electronic constitution selectivity is a huge challenge in photocatalysis. Reported herein is a host-guest interaction strategy to endow photocatalysts with special selectivity. By adjusting the precursors, conjugated macrocycle polymers (CMPs) with pillar[5]arene struts (CMP-1 and CMP-2) and a corresponding non-pillar[5]arene-contained conjugated organic polymer (COP-1) were prepared and the photocatalytic activities toward sulfide derivatives were investigated. The sulfides showed similar conversions when COP-1 was used as a photocatalyst, but exhibited significant differences when it turned to the CMPs. Remarkably, the conversion yield of S-1 achieved near 18 folds over the one of S-2 when CMP-2 was used as a catalyst. Mechanism studies confirmed that the “host-guest” effect of pillar[5]arene struts in CMPs was the main cause of the difference. The present work establishes CMPs as novel heterogeneous photocatalysts with substrate selectivity, and such a method will inspire the researchers concerning preparation of heterogeneous catalysts with excellent selectivity.     

H-β-zeolite catalyzed synthesis of β-bromostyrenes from styrene bromohydrins

Synthesis of β-bromostyrenes from styrene bromohydrins using H-β-zeolite as catalyst under moderate conditions is reported. The catalyst could be regenerated and reused up to three consecutive cycles.     

A theory of flux peaking effect in channeling

The redistribution of the channeled ion flux in the transverse plane has been examined. General formulae describing the flux peaking effect are obtained. Main factors on which the effect depends are investigated. An analysis is made of back-scattering experiments. The study has been made for the axial and planar channeling.     

Continuous segregation of binary heterogeneous solids in a fast-fluidized bed

Continuous segregation of binary heterogeneous solids (different density mixtures) is carried out in a gas–solid fluidized bed to study the effects of gas velocity, solids feed rate, feed composition and density difference of solids on the separation factor (recovery of flotsam at top outlet) and the quality of the product (purity of flotsam at top outlet) in a continuous fast-fluidized bed. The holdup of the bed material is obtained in each experimental run. It is observed that the separation factor decreases with increase in solids feed rate or density difference of solids, and increases with gas velocity or proportion of flotsam in the feed. The quality of the product decreases with increase in gas velocity or solids flow rate, and increases with feed composition or density difference of solids. The experimental results show that the separation factor and the quality of the product are more sensitive to gas velocity than to other operating parameters. Empirical correlations for predicting the separation factor and quality of the product are proposed based on the Richards model for individual flotsam mass fraction in the feed, and the predictions agree satisfactorily with the present experimental data.