Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O-H insertion/base-promoted cyclization involving diazoarylidene succinimides.

A facile approach to novel medicinally relevant spiro heterocyclic scaffolds (namely furan-2(5H)-ones, tetrahydrofurans and pyrans spiro-conjugated with the succinimide ring) has been developed. The protocol consists of Rh(II)-catalyzed insertion of heterocyclic carbenes derived from diazoarylidene succinimides (DAS) into the O-H bond of propiolic/allenic acids or brominated alcohols, followed by base-promoted cyclization to afford the target spirocyclic compounds in good to high yields.

Utilizing Allenic Acids and Heterocyclic Diazo Compounds in the Synthesis of Polysubstituted Spirocyclic Butenolides and ß-Methylidene 2-Furanones.

Herein, we report a novel approach for the assembly of spirocyclic Δα,ß-butenolides and ß-methylidene 2-furanones via Rh(II)-catalyzed O-H insertion of heterocyclic diazo compounds into allenic acids followed by base-promoted cyclization. Utilizing various diazo heterocycles, including α-diazo homophthalimides, 3-diazo tetramic acids, and diazo oxindoles, diverse spirocyclic scaffolds were produced. The research revealed that the allenic acid substitution pattern is decisive for the product type, enabling extraordinary target compound switching between two types of spirocyclic 2-furanones with exo- and endocyclic C═C bonds.

Facile access to 3-sulfonylquinolines via Knoevenagel condensation/aza-Wittig reaction cascade involving ortho-azidobenzaldehydes and ß-ketosulfonamides and sulfones.

Quinoline-based sulfonyl derivatives, and especially sulfonamides, are relevant and promising structures for drug design. We have developed a new convenient protocol for the synthesis of 3-sulfonyl-substituted quinolines (sulfonamides and sulfones). The approach is based on a Knoevenagel condensation/aza-Wittig reaction cascade involving o-azidobenzaldehydes and ketosulfonamides or ketosulfones as key building blocks. The protocol is appropriate for both ketosulfonyl reagents and α-sulfonyl-substituted alkyl acetates providing the target quinoline derivatives in good to excellent yields.

A novel bis-triazole scaffold accessed via two tandem [3 + 2] cycloaddition events including an uncatalyzed, room temperature azide-alkyne click reaction.

The previously described α-acetyl-α-diazomethanesulfonamide was employed in a three-component reaction with azide-containing benzaldehydes and propargylamines. Besides the initial formation of the triazole core, the reaction proceeded further, in uncatalyzed fashion at room temperature and yielded, after intramolecular azide-alkyne click reaction novel, structurally intriguing bistriazoles.

Metal-Free Synthesis of 1,5-Disubstituted 1,2,3-Triazoles.

A three-component synthesis of 1,5-disubstituted 1,2,3-triazoles from α-acetyl-α-diazomethane sulfonamides, primary aliphatic amines, and aromatic aldehydes is presented. The 1,2,3-triazoles can be accessed in two alternative variants, depending on the substitutions in the sulfonamide portion of the diazo reagent. In one variant, intermediate 1,2,3-triazoline-4-sulfonamides are isolated chromatographically and then subjected to thermally promoted aromatization with elimination of sulfur(IV) oxide and amine. In the other variant, both chemical transformations take place in a single step conducted at room temperature.

Chemical and computational strategy for design of "switchable" sorbent based on hydroxyapatite nanoparticles for dispersive micro-solid phase extraction of tetracyclines.

A challenging task in analytical chemistry is an application of renewable and natural materials for isolation of hazardous substances such as antimicrobial drugs from environmental samples. The energy-efficient scalable hydrothermal procedure to fabricate the eco-friendly "switchable" sorbent based on hydroxyapatite nanoparticles with in situ modified surface using a small amount of capping agents was developed. Sorbents characterization including the surface composition investigation via quantum-chemical calculation based on the original approach was provided. The sorbents demonstrated well expressed controllable surface switching and high values of the sorption and elution efficiency for tetracycline, oxytetracycline, and chlortetracycline achieved by simple change of the medium pH. These processes were thoroughly discussed based on the results of chemical and computational experiments. A simple and universal strategy for choosing a suitable sorbent for solid phase extraction of target analytes was proposed for the first time. It was shown that the developed eco-friendly sample preparation procedure with use of biocompatible sorbents could be applied both for removal of target analytes from sample matrix (water samples) as well as for the quantitative analytes determination after elution step. It is believed that the presented research is significant for the determination of different amphoteric analytes in wide variety of samples.