Application of Aminopolycarboxylic Complexes of V(IV) in Catalytic Adsorptive Stripping Voltammetry of Germanium

In the review, voltammetric analytical procedures that employ vanadium(IV) and aminopolycarboxylic complexes of V(IV) are presented and discussed. The focus of the paper is on the mechanism of vanadium-catalyzed reactions responsible for the amplification of the analytical signal of Ge(IV). The analytical efficacy of different catalytic systems is compared, and the optimal parameters of the respective procedures are reported.

Cu-Catalyzed Allylation of Amines with Cyclopropyldiphenylsulfonium Trifluoromethanesulfonate

Cyclopropyldiphenylsulfonium salt is a famous ylide precursor that was previously extensively employed in the preparation of cyclic compounds and has been successfully utilized as an efficient allylation reagent in this work. The Cu-catalyzed reactions of cyclopropyldiphenylsulfonium trifluoromethanesulfonate with amines in the presence of an appropriate ligand provided the N-allylated products in good yields. Aliphatic/aromatic amines and primary/secondary amines were all mildly converted under the reaction conditions. This protocol was also applicable to N-functionalization of drug molecules, supplying the corresponding N-allylated compounds in satisfactory yields. The reaction showed good functional group tolerance, a wide range of substrates, and excellent chemoselectivity, which offered an interesting method for the synthesis of N-allyl amines.

Hygroscopicity of Polycatechol and Polyguaiacol Secondary Organic Aerosol in sub- and supersaturated water vapor environments

Polycatechol and polyguaiacol are light-absorbing and water-insoluble particles that efficiently form from iron-catalyzed reactions with aromatic compounds from biomass burning emissions. Little quantitative information is known about their water uptake...

Chiral Phosphoric Acid Catalyzed Regio- and Enantioselective Reactions of Functionalized Propargylic Alcohols

Propargylic alcohols have been known as useful substrates in a wide range of asymmetric reactions. Particularly, the chiral phosphoric acids (CPAs) catalyzed reactions of functionalized propargylic alcohols opened a robust...

Recent Advances in the Catalytic Applications of Lanthanide-Oxo Clusters

Lanthanide-oxo/hydroxo clusters (LOCs) in this mini-review refer to polynuclear complexes featuring a polyhedral metal-oxo/hydroxo cluster core of lanthanide ions exclusively or with coexisting 3d metal ions. We summarize herein the recent works using this unique family of cluster complexes for catalysis; this aspect of research stands in stark contrast to their extensively studied synthetic and structural chemistry as well as the much-researched magnetic properties. Following a brief introduction of the synthetic strategies for these clusters, pertinent results from available literature reports are surveyed and discussed according to the types of catalyzed reactions. Particular attention was paid to the selection of a cluster catalyst for a specific type of reactions as well as the corresponding reaction mechanism. To the end, the advantages and challenges in utilizing LOCs as multifunctional catalysts are summarized, and possible future research directions are proposed.

Enzyme-catalyzed synthesis of bioactive heterocycles

Enzymes are proteins that functions as biological catalyst. It is now a known fact that enzyme can catalyze many synthetic operations better than the conventional reagents. Not only in the synthesis of natural products, they can also be applied for construction of varieties of unnatural compounds. In this chapter, Pariyar and Ghosh have discussed in brief synthesis of various biologically active heterocyclic compounds using different enzymes as catalysts. Among various enzymes, laccases, trypsin, α-amylase and Bakers’ yeast are few that are easily available and have been extensively explored for various synthetic strategies. This chapter will definitely serve as valuable source of information to the readers in the field of enzyme-catalyzed reactions.

Fine Crystalline Mg-Al Hydrotalcites as Catalysts for Baeyer-Villiger Oxidation of Cyclohexanone with H2O2

The catalytic activity of Mg-Al hydrotalcite (HT) materials in base-catalyzed reactions is known to be promoted by the low crystallinity of the HT solid. In the present work, two routes enabling the preparation of finely crystalline Mg-Al HT materials were explored: (1) the inverse microemulsion technique, and (2) co-precipitation in the presence of starch. Carbonate, chloride and bromide forms of HT were prepared, examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy, and used as catalysts in the Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone with a H2O2/acetonitrile system. The bromide forms proved significantly less active than the chlorides and carbonates, as they promoted nonselective consumption of H2O2. The fine crystalline materials were more active than the more crystalline HT references obtained by conventional co-precipitation. Catalysts prepared by inverse microemulsion were less crystalline and more active than the starch-templated ones, but suffered stronger deactivation by the acidic reaction environment. Alkalization of the reaction medium with NaHCO3 stabilized the HT materials and increased the ε-caprolactone yield, which became comparable for both types of fine crystalline catalysts—thus pointing to the synthesis involving a simple and cheap starch templating approach as being a particularly attractive one.

Hydroformylation

Hydroformylation is one of the most important homogeneously catalyzed reactions on an industrial scale. The manufacture of bulk chemicals clearly dominates. Large cobalt- and rhodium-based processes are mature technologies that have been developed over the past 80 years. Meanwhile, the potential of hydroformylation for the production of fine chemicals (perfumes, pharmaceuticals) has also been recognized. This review gives insight into the state-of-the-art of the reaction and its development. It commences with some remarks on the accidental discovery by the German chemist Otto Roelen within the historical and personal framework of the Fischer–Tropsch process, followed by the mechanistic basics of the catalytic cycle, metals used for the catalyst as well as their organic ligands. In addition, the stability of ligands and catalysts is addressed. The huge potential of this transformation is demonstrated using a variety of substrates. Finally, the use of some surrogates for syngas is discussed.

In vitro biosynthesis of ATP from adenosine and polyphosphate

Adenosine triphosphate (ATP) acts as a crucial energy currency in vivo, and it is a widely used energy and/or phosphate donor for enzyme-catalyzed reactions in vitro. In this study, we established an in vitro multi-enzyme cascade system for ATP production. Using adenosine and inorganic polyphosphate (polyP) as key substrates, we combined adenosine kinase and two functionally distinct polyphosphate kinases (PPKs) in a one-pot reaction to achieve chain-like ATP regeneration and production. Several sources of PPK were screened and characterized, and two suitable PPKs were selected to achieve high rates of ATP production. Among these, Sulfurovum lithotrophicum PPK (SlPPK) exhibited excellent activity over a wide pH range (pH 4.0–9.0) and synthesized ATP from ADP using short-chain polyP. Furthermore, it had a half-life > 155.6 h at 45 °C. After optimizing the reaction conditions, we finally carried out the coupling-catalyzed reaction with different initial adenosine concentrations of 10, 20, and 30 mM. The highest yields of ATP were 76.0, 70.5, and 61.3%, respectively. Graphical Abstract