Recent Advancesin C–H Perfluoroalkyl Thiolationand Perfluoroalkyl Sulfonylation

Biocatalysis is one of the greenest technologies for the synthesis of bioactive molecules, for which the presence of various functional groups requires selective protection or deprotection processes. The effective combination of protecting group techniques often results in additional chemical synthetic steps. At this point, enzymes can prove very valuable, as they help to circumvent several reaction steps, owing to the selectivity they show for a particular group. Specifically, carboxylic acid and alcohol functionalities, as well as esters, are of high importance for the biological properties of certain molecules. Esters are enzyme‐labile moieties, a characteristic that many drugs activity is based on. Ester cleavage is also required for synthesis, where beyond any doubt, the majority of reactions and conditions must be highly selective. This review aims to highlight a number of examples in the literature relative to regio‐ and chemoselective biocatalytic deprotection processes of the carboxyl and hydroxyl moieties, used in the synthesis of pharmaceuticals, bioactive molecules, and drug precursors.

Review: ca. 150 refs.

Hypervalent iodine(III) compounds are known to be exceptionally good oxidizing reagents because they are generally highly reactive, can be used in various molecular designs, and are relatively easy to synthesize and handle. Although they are very useful reagents with a wide range of reactivity, some iodine(III) compounds are difficult to handle due to low solubility and stability issues. In earlier studies, it was found that iodine(III) reagents with an ether group introduced at the ortho-position have improved solubility and stability. Based on these results, new hypervalent iodine compounds were developed by utilizing coordinating properties of functional groups other than the ether group. In this paper, hypervalent iodine compounds with carboxyl or hydroxyl groups introduced into the aromatic ring attached to the iodine atom were successfully synthesized, and their structures were elucidated by X-ray structural analysis. In addition, the reactivity of these compounds is reported based on the successful development of several unique reactions.

The orthoester Johnson–Claisen rearrangement, an important C–C bond forming reaction, has been used enormously in the past four decades in the synthesis of bioactive molecules, natural products, synthetic intermediates, analogues, and useful building blocks. The method has also featured in chemical modification of materials. This review covers developments in this rearrangement since 2003. Unlike many other forms of Claisen rearrangement, this reaction is generally a one‐pot, one‐step process. It is compatible with numerous functional groups, despite its use of acid catalysis, and offers chirality transfer to produce stereoselective products. The method also offers opportunities for rapid modifications to various functionalized compounds and building blocks for further synthetic exploration.

Review: [211 refs.

DEVELOPMENT IN GLYCOSYLATION METHODS: A KEY TO ACCESS ITS APPLICATIONS IN THE SYNTHESIS OF BIOACTIVE MOLECULES. Glycosylation reaction is an important class of reactions in organic chemistry, and the development of the method contributes to the synthesis of many biologically active compounds containing various glycoside bonds. Is arguably the most important, albeit challenging, reaction in the field of carbohydrate chemistry. Examples of the products of glycosylation reactions are glycoproteins, glycolipids, glycosaminoglycans, oligosaccharides, and polysaccharides. Glycosylation types are classified according to the identity of the atom which binds the carbohydrate chain, i.e. C-linked, N-linked, O-linked or S-linked. In this short review, recent reports of the main glycosylation methods, basic mechanisms, factors influencing the stereoselectivity and their applications in the synthesis of bioactive molecules are described.

Drug discovery and quality evaluation are very important for human health. Drugs from chemical synthesis and natural products are a very important branch in drug discovery. The highly efficient synthetic methodology development and pharmacological evaluation of related active agents, as essential steps to developing corresponding innovative drugs, are always research frontiers for organic chemists and medicinal chemists. Meanwhile, the drug quality evaluation is an important guarantee for the clinical application of drugs and the efficacy of drugs. Therefore, we wanted to organize this article collection for the presentation of the high-quality work from internationally recognized researchers to promote academic communication among scientific researchers focusing on medicinal and pharmaceutical chemistry. In recent years, the research community has witnessed significant advances in the development of the discovery of novel natural products, design and synthesis of bioactive molecules, synthetic methodology, and drug quality evaluation. Therefore, we hope to be able to summarize and display the latest developments in the design and synthesis of bioactive molecules, synthetic methodologies, the discovery of novel natural products, as well as drugs quality evaluation through the collection of this album, and provide new methods and template molecules for the subsequent development of innovative drug molecules.

The rational design of novel bioactive molecules is a critical but challenging task in drug discovery [...].

The sulfuration of unreactive carbon-hydrogen bonds stands as one of the significant breakthroughs in organic synthetic chemistry in recent years. This methodology enables the efficient construction of C-S bonds through direct activation of high bond energy C-H bonds, substantially enhancing both synthetic efficiency and atom economy for sulfur-containing compounds. This review systematically summarizes the strategic progress in unreactive C-H bond sulfuration, encompassing core methodologies such as transition-metal catalysis, photocatalytic systems, and electrocatalytic systems. It analyses the sulfur source activation mechanisms under different catalytic modes, the kinetic and thermodynamic driving forces for C-H bond cleavage, and the regulatory principles of site selectivity. Furthermore, it compiles application examples in late-stage sulfuration modification of complex molecules, construction of chiral sulfur centres, and synthesis of bioactive molecules within this field.

The azidofunctionalization of alkenes has emerged as a powerful difunctionalization strategy, expanding the toolbox of synthetic chemistry. This transformation enables the simultaneous installation of an azide and a second functional group onto an alkene, facilitating access to diverse nitrogen‐containing compounds. The azidofunctionalization is particularly valuable in pharmaceutical and materials chemistry, as azides serve as key intermediates in the synthesis of bioactive molecules and polymers. Various catalytic and radical‐mediated approaches are developed. Photoredox catalysis, transition metal‐mediated reactions, and hypervalent iodine chemistry have enabled regio‐ and stereoselective transformations under mild conditions. Radical‐mediated methods, in particular, provide high efficiency and broad substrate scope, enabling the incorporation of azide groups even in complex molecular scaffolds. Recent advances have also explored enantioselective azidofunctionalization using chiral catalysts, opening new opportunities for the asymmetric synthesis of nitrogen‐containing derivatives. This review provides a comprehensive overview of azidofunctionalization methodologies, highlighting the diverse functional groups that have been introduced in a single‐step alongside an azide.

Synthesis of seven-membered carbocycle-fused aromatics was realized by Catellani reaction using terminally brominated alkyl carbagermatranes through intermolecular cyclization manner. Various functional groups were well tolerated, and this transformation was also expanded to the synthesis of carbocycles of other size. The utility of this method was demonstrated by modification of natural product derivatives and synthesis of bioactive molecules.

Hypervalent (HV) iodine(III) compounds with fluorine-containing ligands (F, CF3, C6F5CO2, or CF3(CF2)8CO2 (n-C9F19CO2)) reacted, in the presence of iodine or copper salts, with the double bonds in ...

Ph(R)IF⋯HF (R = Me, Et, iPr, tBu) interaction: A strong hydrogen bond between hypervalent iodine compounds and HF

Alkyl chlorides are a class of versatile building blocks widely used to generate C(sp3)-rich scaffolds through transformation such as nucleophilic substitution, radical addition reactions and metal-catalyzed cross-coupling processes. Despite their utility in the synthesis of high-value functional molecules, distinct methods for the preparation of alkyl chlorides are underrepresented. Here, we report a visible-light-mediated dual catalysis strategy for the modular synthesis of highly functionalized and structurally diverse arylated chloroalkanes via the coupling of diaryliodonium salts, alkenes and potassium chloride. A distinctive aspect of this transformation is a ligand-design-driven approach for the development of a copper(II)-based atom-transfer catalyst that enables the aryl-chlorination of electron-poor alkenes, complementing its iron(III)-based counterpart that accommodates non-activated aliphatic alkenes and styrene derivatives. The complementarity of the two dual catalytic systems allows the efficient aryl-chlorination of alkenes bearing different stereo-electronic properties and a broad range of functional groups, maximizing the structural diversity of the 1-aryl, 2-chloroalkane products.

One-step conversion of xylose to furfuryl alcohol on sulfated zirconia-supported Pt catalyst—Balance between acid and metal sites