Spirocyclic compounds are of increasing importance owing to their potential applications in the development of new pharmaceuticals. Herein, we describe a new, rapid access to rarely seen spirooxazolines utilizing an I(I)/I(III) reaction manifold. The scope of the cyclization using phenols and naphthols is described along with the stereoselective functionalization of the spirocycles. The application

We developed a one‐pot two‐step deracemization approach for alcohols using two mutants of Thermoanaerobacter pseudoethanolicus secondary alcohol dehydrogenase ( Te SADH). This approach relies on consecutive non‐stereospecific oxidation of alcohols and stereoselective reduction of their prochiral ketones using two mutants of Te SADH with poor and good stereoselectivities, respectively. More specifically

A series of GABA analogs and related mono‐ and bifunctional building blocks based on the monofluorinated 1,3‐disubstituted cyclobutane scaffold was designed and synthesized. The synthetic approaches included desilylative deoxyfluorina­tion of TMS‐protected cyanohydrin and iodofluorination of methy­lenecyclobutane carboxylate as the key steps. Both approaches were highly efficient for the multigram

Fluoroalkyl(hetero)arylation of allylic alcohols with perfluoroalkyl iodide or difluoroacetic acid as fluoroalkyl source was developed herein, delivering antibacterial ketones containing an α‐quaternary center. Formation of the fluoroalkyl radical was followed by its intermolecular addition to alkenes and the migration of a (hetero)aryl group with the concomitant generation of a carbonyl functionality

Phosphorus – sp3 or sp2 carbon bonds are readily formed by the reaction of bis‐diazaphospholenes with several classes of electrophiles. These reactions result in cleavage of the phosphorus‐phosphorus bond and formation of functionalized diazaphospholenes. The reactions proceed rapidly, without catalysis. Experimental evidence with aryl and alkyl halides suggests the intermediacy of radicals in some

Among the wide variety of heterocycles, 2‐oxazolidinones are recognized as some of the most important heterocyclic compounds in medicinal chemistry. Therefore, the development of a practical methods for their synthesis would be an important development. Herein, we report a practical method for the synthesis of 2‐oxazolidinones under solvent‐free conditions using triethylamine hydroiodide as a simple

The first‐time reported nitrogen source‐based chemoselectivity of Dehydroacetic acid (DHA)‐derived enones has been tuned by Isoniazid (INH), and phenylhydrazines respectively. When INH a first‐line antitubercular drug, was employed as a new surrogate for nitrogen source, preferentially unconventional 1,3‐dicarbonyl addition occurred, providing a series of fused 3‐styryl pyrano[2,3‐ c ]pyrazolones in

A new approach for the synthesis of highly pharmaceutically relevant 4‐fluoropyrazoles via oxidative annulation of α‐fluoronitroalkenes with in situ prepared hydrazones was developed. The reaction is efficiently promoted by trifluoroacetic acid while atmospheric oxygen was used as an oxidant. Broad substrate scope was demonstrated. Both electron‐rich and electron‐deficient nitroalkenes as well as different

An efficient total synthesis of ceratopicanol was achieved through successive Pd catalyzed reductive cycloaddition and cyclization reactions. The Pd mediated cyclization reaction to form a triquinane structure demonstrated that a small structural difference changed the reaction pathway either to form different structures or reduced non‐cyclized product depending on the reaction conditions.

An investigation of the unexpected lability of the Csp3 ‐Csp2 bond connecting 2,4,6‐trimethoxyphenyl group and an allylic moiety is carried out. We observed that the catalytic presence of either Lewis or Brønsted acid can render such 2,4,6‐trimethoxyphenyl group labile. Several nucleophiles were found to substitute the labile C‐C bond in mild reaction conditions resulting in very good yields of the

Two diastereomers of the title compound were synthesized through an enantioselective route, with the stereogenic center at the C‐2 derived from a commercially available reagent and the one at the C‐4 installed via Evans asymmetric aldol condensation. By comparison of 1 H and 13 C NMR as well as optical rotations the configuration of the natural product was as assigned as (2 R ,4 R ). Some interesting

The treatment of the TBS‐protected p ‐toluenesulfonimidamide with HCl exclusively affords the deprotected product. However, when HCl was replaced with formic acid, and the reaction mixture was left for extended time or treated at high temperature, a mixture of oligomers was obtained as main products. The relevant N,N’‐capped oligomers were prepared through carbamoylation with p ‐chlorophenyl isocyanate

A simple protocol for the regioselective N‐arylation of the indole side chain of tryptophan using triarylbismuth reagents as the arylating agent is reported. The reaction is catalyzed by copper(II) acetate, operates in the presence of triethylamine or pyridine under air at 50 °C, allows the transfer of aryl groups bearing electron neutral, donating or withdrawing substituents at any position of the

The first enantioselective total synthesis of cassane‐type furanoditerpenoids featuring an aromatic C ring and a substituted B ring is presented. The strategy employed relied on diastereoselective Diels–Alder (DA) reaction of a an enantiomerically pure 1,3,3‐trisubstituted‐2‐vinyl‐cyclohexene (sterically demanding diene). It was secured in > 99% ee through elaboration of enzymatically resolved 3‐e

1,3,5‐Trisubstituted 2,4,6‐triethylbenzenes consisting of isopropyl groups as recognition units have previously been shown to have interesting binding properties towards selected carbohydrates. The design of such artificial carbohydrate receptors was inspired by the mode of action of carbohydrate‐binding proteins, namely by the participation of the isopropyl side chain of valine in the formation of

Two consecutive three‐component syntheses furnishing β‑amino enoates or 3‐hydroxypyrazoles based upon the Sonogashira alkynylation of aryl iodides and ethyl propiolate were established in mostly excellent yields. The ethyl 3‐arylpropiolate intermediates are Michael systems and excellently suited for concatenation with conjugate addition or cyclocondensation giving access to libraries of 21 different

A four‐step approach to the ‘hydrated imidazoline ring expansion’ (HIRE) is presented. In most cases, the ring expansion was the sole process. However, for the first time, an alternative course of the hydrated imidazoline evolution was discovered which gave N ‐aminoethyl derivatives. These can, in principle, be converted to the target HIRE products under sufficiently forcing conditions. The approach

The 1,3‐dipolar cycloadditions of azomethine‐ylides and ‐imines, nitrones, nitrilimines and azides catalysed by inorganic nanoparticles are described. Emphasis is given to the nanometric catalysts involved, their structure, characterisation, and recyclability and, when remarkable, their preparation. Whenever possible, the improvements with respect to cycloadditions performed with the usual (non‐nano)

We report a convenient short synthesis of tricyclic guanidine‐containing natural products model featuring four‐component reaction between 2,5‐dimethoxytetrahydrofuran, 2‐aminopyrimidine and two acylacetic or benzoylacetic acids. A synthetic route combining the Robinson‐Schöepf bioinspired strategy and biomechanistic analysis of the crambescidin and batzelladine alkaloids family. An application of this

Synthesis of orthogonally protected 2‐silyl nucleosides were achieved by trans opening of sugar epoxides with nucleobases catalyzed by trimethylsilyl trifluoromethanesulfonate using hexamethyldisilazane both as solvent and silylating agent. Both α and β nucleosides were obtained with complete stereocontrol only by changing the epoxide stereochemistry. The synthesized nucleosides exist in different

A spirocyclopropanation of para ‐quinone methides with 3‐chlorooxindoles that proceeds via cascade 1,6‐conjugate addition/dearomatization reaction has been established, leading to a novel class of bis‐spiro compounds in a concise, rapid, and practical manner. This transformation could be completed in high yields at room temperature within five minutes. The resulting bis‐spiro cyclopropane derivatives

Five‐membered heteroarenes constitute ubiquitous moieties in bioactive compounds and materials. It is thus not surprising that a direct and selective access to multiply substituted heteroarenes is considered as a highly attractive synthetic target. The direct olefination of such substrates, also known as cross‐dehydrogenative coupling has raised significant interest in this context. However, achieving

Reacting parabanic acid with the superacidic systems X F/ M F 5 ( X = H, D; M = As, Sb) in different ratios, led to the formation of the mono‐ and diprotonated species. Salts in terms of [C 3 H 3 N 2 O 3 ][AsF 6 ], [C 3 H 3 N 2 O 3 ][SbF 6 ], [C 3 H 4 N 2 O 3 ][AsF 6 ] 2 , [C 3 H 4 N 2 O 3 ][SbF 6 ] 2 , [C 3 D 3 N 2 O 3 ][AsF 6 ] and [C 3 D 4 N 2 O 3 ][AsF 6 ] 2 were obtained and characterized by low‐temperature

Visible‐light‐mediated chemical reactions have become enormously popular within the last ten years. This review covers the recent developments in visible‐light photofunctionalization of quinoxalin‐2‐one derivatives. Reaction types have been categorized depending on the kind of bond formed: C‐C, C‐O, C‐N, C‐S, C‐P and C‐X, with representative examples and discussion on the catalyst used providing insightful

A novel synthetic path to 1,3‐disubstituted pyrazoles and their deuterated derivatives was developed. It is based on the reaction of vinyl ethers with hydrazonoyl chlorides in the presence of triethylamine. The reaction mechanism, clarified by the joint experimental and computational study, involves 1,3‐dipolar cycloaddition of the in situ generated nitrile imines to vinyl ethers and subsequent cleavage