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.

Bronsted acidic surfactants: efficient organocatalysts for diverse organic transformations

Organic transformations using efficient, atom-economical, cost-effective and environmentally benign strategies for the construction of diversified molecules have attracted synthetic chemists worldwide in recent years. These processes often minimize the waste production and avoid the use of hazardous flammable organic solvents. Among various green protocols, the procedures using surfactant-based catalytic systems have received a considerable attention in organic synthesis. In this context, Bronsted acidic surfactants have emerged as efficient catalysts for various C–C, C–O, C–N and C–S bond forming reactions. Many of these reactions occur in water, as Bronsted acidic surfactants have a unique ability of creating hydrophobic pocket through micelle formation in aqueous medium and the substrate molecules react efficiently to afford the targeted products in good yields. In the past, Bronsted acidic surfactant combined catalysts successfully displayed their potential to accelerate the reaction rates of diverse organic transformations. This chapter presents a complete overview on Bronsted acidic surfactants catalyzed organic reactions to construct a variety of aromatic and heteroaromatic molecular frameworks.

Selectivity Control of C-O Bond Cleavage for Catalytic Biomass Valorization

Increasing fossil fuels consumption and global warming have driven the global revolution towards renewable energy sources. Lignocellulosic biomass is the main source of renewable carbon-based fuels. The abundant intermolecular linkages and high oxygen content between cellulose, hemicellulose, and lignin limit the use of traditional fuels. Therefore, it is a promising strategy to break the above linkages and remove oxygen by selective catalytic cracking of C–O bond to further transform the main components of biomass into small molecular products. This mini-review discusses the significance of selectivity control in C–O bond cleavage with well-tailored catalytic systems or strategies for furnishing biofuels and value-added chemicals of high efficiency from lignocellulosic biomass. The current challenges and future opportunities of converting lignocellulose biomass into high-value chemicals are also summarized and analyzed.

Photoinitiated Multicomponent Anti-Markovnikov Alkoxylation over Graphene Oxide

The development of graphene oxide–based heterogeneous materials with an economical and environmentally–friendly manner has the potential to facilitate many important organic transformations but proves to have few relevant reported reactions. Herein, we explore the synergistic role of catalytic systems driven by graphene oxide and visible light that form nucleophilic alkoxyl radical intermediates, which enable an anti-Markovnikov addition exclusively to the terminal alkenes, and then the produced benzyl radicals are subsequently added with N–methylquinoxalones. This photoinduced cascade radical difunctionalization of olefins offers a concise and applicable protocol for constructing alkoxyl–substituted N–methylquinoxalones.

Selective Hydrogenation Properties of Ni-Based Bimetallic Catalysts

Metallic Ni shows high activity for a variety of hydrogenation reactions due to its intrinsically high capability for H2 activation, but it suffers from low chemoselectivity for target products when two or more reactive functional groups are present on one molecule. Modification by other metals changes the geometric and electronic structures of the monometallic Ni catalyst, providing an opportunity to design Ni-based bimetallic catalysts with improved activity, chemoselectivity, and durability. In this review, the hydrogenation properties of these catalysts are described starting from the typical methods of preparing Ni-based bimetallic nanoparticles. In most cases, the reasons for the enhanced catalysis are discussed based on the geometric and electronic effects. This review provides new insights into the development of more efficient and well-structured non-noble metal-based bimetallic catalytic systems for chemoselective hydrogenation reactions.

The Effect of Chemical Representation on Active Machine Learning Towards Closed-Loop Optimization

Multivariate chemical reaction optimization involving catalytic systems is a non-trivial task due to the high number of tuneable parameters and discrete choices. Closed-loop optimization featuring active Machine Learning (ML) represents a powerful strategy for automating reaction optimization. However, the translation of chemical reaction conditions into a machine-readable format comes with the challenge of finding highly informative features which accurately capture the factors for reaction success and allow the model to learn efficiently. Herein, we compare the efficacy of different calculated chemical descriptors for a high throughput generated dataset to determine the impact on a supervised ML model when predicting reaction yield. Then, the effect of featurization and size of the initial dataset within a closed-loop reaction optimization was examined. Finally, the balance between descriptor complexity and dataset size was considered. Ultimately, tailored descriptors did not outperform simple generic representations, however, a larger initial dataset accelerated reaction optimization.

Isolated Neutral [4]Helicene Radical Provides Insight into Consecutive Two-Photon Excitation Photocatalysis

Direct activation of strong bonds in readily available, benchtop substrates offer a straightforward simplification, albeit in most cases existing catalytic systems are limited to unlock such activation. In recent years, a surge of in-situ generated organic radicals that can act as potent photoinduced electron transfer (PET) agents have proved to be a powerful manifold for the activation of remarkably stable bonds. Herein we document the use of N,N′-di-n-propyl-1,13-dimethoxyquinacridine (nPr-DMQA•), an isolated and stable neutral helicene radical, as a highly photoreducing species. This isolable doublet state open shell radical offers a unique opportunity to shed light on the mechanism behind PET reactions of organic radicals. Experimental and spectroscopic studies revealed that this doublet radical has a long lifetime of 4.6 ± 0.2 ns, an estimated excited state oxidation potential of -3.31 V vs SCE, and can undergoes PET with organic substrates. The strongly photoreducing nature of the nPr-DMQA• was experimentally confirmed by the demonstration of photo activation of electron rich aryl bromides and chlorides. We further demonstrated that nPr-DMQA• can be photochemically generated from its cation analog (nPr-DMQA+) allowing catalytic functionalization of aryl halide via a consecutive photoexcitation mechanism (ConPET). Dehalogenation, photo-Arbuzov, photo-borylation and C-C bond formation reactions with aryl chlorides and bromides are reported herein, as well as the α-arylation of carbonyl using cyclic ketones. The latter transformation exhibits the facile synthesis of α-arylated cyclic ketones as critical feedstock chemical for diverse useful molecules, especially in the biomedical enterprises.

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge 1–3. This is particularly true in the context of accessing non-natural reactions by bioinspired approaches, which offer intriguing possibilities for benign and affordable chemical synthesis 4. Exploiting the untapped potential of inorganic solids by translating complex knowledge in (bio)molecular-based systems may constitute a potentially useful strategy for such purpose 5, but efforts to capitalize on the minimum catalytic unit of a versatile solid matrix have been largely unsuccessful. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighboured single cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

Mimicking Enzymes: Taking Advantage of the Substrate-Recognition Properties of Metalloporphyrins in Supramolecular Catalysis

The present review describes the most relevant advances dealing with supramolecular catalysis in which metalloporphyrins are employed as substrate-recognition sites in the second coordination sphere of the catalyst. The kinetically-labile interaction between metalloporphyrins (typically, those derived from zinc) and nitrogen- or oxygen-containing substrates is energetically comparable to those non-covalent interactions (i.e. hydrogen bonding) found in enzymes enabling substrate-preorganization. Much inspired from this host-guest phenomena, the catalytic systems described in this account display unique activities, selectivities and action modes difficult to reach applying purely covalent strategies.

CO2 Reduction on Single-Atom Ir Catalysts with Chemical Functionalization

As promising catalytic systems, single-atom catalysts (SACs) demonstrate improved catalytic performance for electrochemical reactions. However, the pinning of metal atoms on surfaces usually depends on the adsorption on defects. In...