Visible Light-Induced Aerobic Oxidative Dehydrogenation of C–N/C–O to C=N/C=O Bonds Using Metal-Free Photocatalysts: Recent Developments

Performing synthetic transformation using visible light as energy source, in the presence of a photocatalyst as a promoter, is currently of high interest, and oxidation reactions carried out under these conditions using oxygen as the final oxidant are particularly convenient from an environmental point of view. This review summarizes the recent developments achieved in the oxidative dehydrogenation of C–N and C–O bonds, leading to C=N and C=O bonds, respectively, using air or pure oxygen as oxidant and metal-free homogeneous or recyclable heterogeneous photocatalysts under visible light irradiation.

Cleavage via Selective Catalytic Oxidation of Lignin or Lignin Model Compounds into Functional Chemicals

Lignin, a complex aromatic polymer with different types of methoxylated phenylpropanoid connections, enables the sustainable supply of value-added chemicals and biofuels through its use as a feedstock. Despite the development of numerous methodologies that upgrade lignin to high-value chemicals such as drugs and organic synthesis intermediates, the variety of valuable products obtained from lignin is still very limited, mainly delivering hydrocarbons and oxygenates. Using selective oxidation and activation cleavage of lignin, we can obtain value-added aromatics, including phenols, aldehydes, ketones, and carboxylic acid. However, biorefineries will demand a broad spectrum of fine chemicals in the future, not just simple chemicals like aldehydes and ketones containing simple C = O groups. In particular, most n-containing aromatics, which have found important applications in materials science, agro-chemistry, and medicinal chemistry, such as amide, aniline, and nitrogen heterocyclic compounds, are obtained through n-containing reagents mediating the oxidation cleavage in lignin. This tutorial review provides updates on recent advances in different classes of chemicals from the catalytic oxidation system in lignin depolymerization, which also introduces those functionalized products through a conventional synthesis method. A comparison with traditional synthetic strategies reveals the feasibility of the lignin model and real lignin utilization. Promising applications of functionalized compounds in synthetic transformation, drugs, dyes, and textiles are also discussed.

New Nitrogen, Sulfur-, and Selenium-Donating Ligands Derived from Chiral Pyridine Amino Alcohols. Synthesis and Catalytic Activity in Asymmetric Allylic Alkylation

Although many chiral ligands for asymmetric catalysis have been developed, there is still a need for new structures allowing the modular approach. Recently, easy synthesis of chiral pyridine-containing β-amino alcohols has been elaborated by opening respective epoxides with enantiomeric 1-phenylethylamine. This paper reports the synthetic transformation of β-amino alcohols into the new complexing pyridine-containing seleno- and thioethers. The amino alcohols were effectively converted to cyclic sulfonamidates, which were reacted with thiolates or phenyl selenide nucleophile. The reaction was diastereoselective, and its outcome depended on the configuration at the substitution center. The problem was discussed considering DFT optimized structures of both diastereomeric sulfonamidates. New amino-aldimine ligands were also synthesized from chiral pyridine-containing diamines. Nine new chiral ligands were tested in the Tsuji-Trost allylic alkylation resulting in the enantiomerically enriched product in up to 75% ee. The observed stereochemical induction agrees with the prevailing nucleophilic attack at the allylic carbon laying opposite to the complexing nitrogen of pyridine in η3-allylic intermediate complexes.

Sustainable synthesis of CO2-derived polycarbonates from d-xylose

Synthetic transformation of d-xylose into a four-membered cyclic ether allows for reactions with CO2 leading to linear polycarbonates by either ring-opening copolymerisation directly or by isolation of a six-membered cyclic carbonate followed by ring-opening polymerisation.

Microbial Oxidoreductases: Biotechnological and Synthetic Applications

Enzymes are biocatalysts responsible for driving all biochemical reactions in the cells. The enzymes determine the physiology of a cell and together regulate the growth and proliferation of cells in response to various environmental signals. The ability of cells to adapt and respond to environmental conditions can be utilized for industrial applications. Hydrolases and oxidoreductases are the most common classes of enzymes used in various industries such as pharmaceutical, food and beverages, bioremediation and biofuels, among others. Oxidoreductases are the EC1 class enzymes that catalyze the biological oxidation and reduction reactions. They transfer electrons from one molecule (reductant that donates electron) to other molecules (oxidants those accept electron). Usually, the enzymes of this class are NAD+ (Nicotinamide Adenine Dinucleotide) or NADP (Nicotinamide Adenine Dinucleotide Phosphate)-dependent. The oxidoreductases are a diverse class of enzymes responsible for catalyzing highly stereo selective and regioselective reactions, because of which they are the enzymes of choice for synthesis of optically-active compounds. Alcohol dehydrogenase (ADH) is one of the most studied oxidoreductases. Generally, ADHs have narrow specificity towards their substrates. Here we are looking for ADH having high/ broad specificity towards the substrate. This review discusses the enzyme oxidoreductase, synthetic transformation with oxidoreductase and application of oxidoreductase in bioremediation.

Synthesis of 2-Benzylidene-3-Pyrrolines and Their Synthetic Transformation

A series of benzylidene-3-pyrrolines were prepared from chalcone derivatives, arylacetylene and sulfonamide via a three-step sequence without the isolation of intermediates. Typically, the reaction of 1,3-di-p-tolylprop-2-en-1-one with lithium phenylacetylide was followed by substitution with tosylamide and then silver-catalyzed 5-exo-dig cyclization to give N-tosyl-2-benzylidene-3,5-di-p-tolyl-2,5-dihydro-1H-pyrrole with a 86% yield. Furthermore, transformation to the corresponding substituted 3-pyrrolin-2-one and pyrrole by m-chloroperbenzoic acid (mcpba)-oxidation and acid-catalyzed aromatization, respectively, was investigated.

Expanding Reactivity in DNA-Encoded Library Synthesis via Reversible Binding of DNA to an Inert Quaternary Ammonium Support

Herein, we present the adaptation of reversible adsorption to solid support (RASS) for a DEL setting, which allows reactions to be performed in organic solvents at near anhydrous conditions opening previously inaccessible chemical reactivities to DEL. The RASS approach enabled the rapid development of C(sp²)-C(sp³) decarboxylative cross-couplings with broad substrate scope, an electrochemical amination (the first electrochemical synthetic transformation performed in a DEL context), and improved reductive amination conditions. We believe that RASS will offer expedient access to new DEL reactivities, expanded chemical space, and ultimately more drug-like libraries.