Abstract Copper‐catalyzed Si−H, B−H, P−H, S−H, and N−H insertion reactions of 2,2,2‐trifluoro‐1‐diazoethane 1‐aryl 2,2,2‐trifluorodiazoethanes generated a large number new fluorine‐containing chemical entities for medicinal chemists. With selected Si−H B−H reactions, we demonstrate successful extension to asymmetric catalysis.

A simple process for the oxy-monofluoromethylation of alkenes is described. In combination with visible-light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source monofluoromethyl (CH2 F) radical, enabling step economical synthesis γ-fluoro-acetates from broad range olefinic substrates under mild conditions. Applications to late-stage diversification derived complex molecules, amino acids and...

Abstract Fluoroalkyl ethers have attracted considerable research interest in the fields of pharmaceutical, agrochemical, nuclear imaging and material sciences, forging development new synthetic methods to access this class compounds. Radical fluoroalkoxylation has recently emerged as a promising approach for synthesizing fluoroalkyl ethers. Herein, solid, easy‐to‐access redox‐active N−O reagent, 1‐(fluoromethoxy)‐3‐methyl‐benzotriazolium triflate (FMBT), serving radical source...

Abstract Copper‐catalyzed Si−H, B−H, P−H, S−H, and N−H insertion reactions of 2,2,2‐trifluoro‐1‐diazoethane 1‐aryl 2,2,2‐trifluorodiazoethanes generated a large number new fluorine‐containing chemical entities for medicinal chemists. With selected Si−H B−H reactions, we demonstrate successful extension to asymmetric catalysis.

The synthesis of organofluorine compounds is vital in developing innovative pharmaceuticals, materials, and agrochemicals. Fluorinated carbene transfer offers a promising strategy for forming new carbon-carbon carbon-heteroatom bonds, facilitating the incorporation fluorine into target structures. In this study, we introduce novel fluoroacetyl sulfonium reagent, (2-ethoxy-1-fluoro-2-oxoethyl)(phenyl)(2,3,4,5-tetramethylphenyl)sulfonium tetrafluoroborate (1), serving as an effective...

The synthesis of organofluorine compounds is vital in developing innovative pharmaceuticals, materials, and agrochemicals. Fluorinated carbene transfer offers a promising strategy for forming new carbon-carbon carbon-heteroatom bonds, facilitating the incorporation fluorine into target structures. In this study, we introduce novel fluoroacetyl sulfonium reagent, (2-ethoxy-1-fluoro-2-oxoethyl)(phenyl)(2,3,4,5-tetramethylphenyl)sulfonium tetrafluoroborate (1), serving as an effective...

Acridinium salts are well-known and highly effective organic photoredox catalysts, particularly recognized for their strong oxidizing properties. While they widely used as photo-oxidants, potential photo-reductants, formed easily through interactions with electron donors-has been largely overlooked underexplored in photocatalysis. In this study, we describe the application of acridinium salt photocatalyst reductive activation iodine(III) reagents containing monofluoroacetoxy ligands. This...

Halogen-atom transfer (XAT) is an effective method for generating carbon radicals from alkyl halides. While stannanes and silanes have shown potential, their toxicity secondary reactivity necessitate the search better alternatives. Recently, carbon-based α amino emerged as possible substitutes; however, generation under photochemical conditions requires use of photocatalysts. In this work, we present a novel XAT that eliminates need photocatalysts by utilizing direct excitation...

A kinetically directed, stepwise approach towards molecular Borromean links enabled the isolation and structural characterization of synthetic intermediates along way.

Diarylfluoromethylsulfonium salts, alternatives to freons or advanced fluorinated building blocks, are bench stable and easy-to-use sources of direct fluoromethylene (:CHF) transfer alkenes. These salts enabled development a trans-selective monofluorinated Johnson-Corey-Chaykovsky reaction with vinyl sulfones sulfonamides access synthetically challenging monofluorocyclopropane scaffolds. The described method offers rapid cyclopropane blocks further functionalization opportunities deliver...

Diarylfluoromethyl sulfonium salts are efficient fluoromethylene transfer reagents equivalent to fluorocarbene, which is difficult access. This was demonstrated by the development of a monofluorinated Johnson-Corey-Chaykovsky reaction with ketones and aldehydes, delivering uncommon 2-unsubstituted fluoroepoxides. first evidence for feasibility sulfur fluoromethylylide its action as intermediate.

A nuclear magnetic resonance (NMR) spectrometer is a key instrument in the organic synthesis laboratory for structure determination, reaction control, and compound purity analysis. In addition to qualitative analysis, application of NMR quantitative analysis (qNMR) gaining popularity. qNMR allows simple quantification crude product mixtures, determination yields, compounds. The yield requires an internal standard each sample. Herein, we report method where CDCl3 residual solvent signal used...

Herein we report an approach for the straightforward preparation of fluorocyclopropylidene group from aldehydes and ketones via Julia-Kocienski olefination using newly developed reagent 5-((2-fluorocyclopropyl)sulfonyl)-1-phenyl-1H-tetrazole. Derivatization monofluorocyclopropylidene compounds includes hydrogenation to deliver fluorocyclopropylmethyl fluorinated cyclobutanones. The utility described method is demonstrated by synthesis a fluorocyclopropyl-containing analogue ibuprofen....

Combination of five- and six-membered rings allows creation 2,2′:6′,2′′-terpyridine derivatives mimicking the topology 5,5′-functionalized 2,2′-bipyridine. This molecular design led to assembly heterometallic supramolecular networks.

Synthesis of double-threaded ruthenium(<sc>ii</sc>) ring-in-ring complexes and the Borromean link with three unequal rings detected by mass spectrometry.

The synthesis of five-membered rings using fluoromethylene transfer chemistry is an attractive method for building fluorinated products high value. This work demonstrates the first time that one-fluorine-one-carbon modification a substrate could be viable strategy to access monofluorinated rings. synthetic methodology was developed isoxazoline-N-oxides in one step starting from substituted 2-nitroacrylates fluoromethylsulfonium reagents.

We report a photo-redox catalyzed radical C–H monofluoromethylation of heterocycles, thus demonstrating this process and the importance monofluoromethyl unit in medicinal drug discovery purposes.

A fluorocyclopropanation of double activated alkenes with a diarylfluoromethylsulfonium reagent is an efficient approach to obtain range monofluorocyclopropane derivatives.

An investigation of the properties and reactivity fluoromethylsulfonium salts resulted in redesign reagents for fluoromethylene transfer chemistry. The model reaction, fluorocyclopropanation nitrostyrene, turned out to be a suitable platform discovery more streamlined reagents. incorporation halides on one aryl ring increased reactivity, 2,4-dimethyl substitution other provided balance between reactivity/crystallinity reagent as well atom economy. utility new was demonstrated by development...

Abstract Monofluoromethylsulfonium salts are emerging reagents for the fluoromethylation and fluoromethylenation or fluoromethylene transfer. Using this type of reagent is a simple approach introduction fluoromethyl group into wide range nucleophiles using mild basic conditions. Recently, fluoromethylsulfonium have been demonstrated to act as synthetic equivalent challenging synthon. For instance, these can be used direct synthesis monofluoroepoxides fluorocyclopropanes from activated...

Synthesis of fluoroorganic compounds is great importance due to their extensive application in medicinal chemistry, agrochemicals, and materials. Herein, we report efficient synthesis novel diaryl fluorohalomethyl sulfonium salts. The showcased proficient reagents for Freon-free fluorochloro-, fluorobromo-, fluoroiodocarbene transfer alkenes. developed mild, room temperature conditions the cyclopropanation do not require any metal catalysts allow synthetic access diverse cyclopropanes.

Abstract A simple process for the oxy‐monofluoromethylation of alkenes is described. In combination with visible‐light copper(I) photoredox catalysis, an easily accessible iodine(III) reagent containing monofluoroacetoxy ligands serves as a powerful source monofluoromethyl (CH 2 F) radical, enabling step economical synthesis γ ‐fluoro‐acetates from broad range olefinic substrates under mild conditions. Applications to late‐stage diversification derived complex molecules, amino acids and...

Metal complexes of linear bilateral extended 2,2′:6′,2″-terpyridine [2,6-bis(2-substituted furo[2,3-c]pyridin-5-yl)pyridine] are topological tridentate analogues 5,5′-functionalized 2,2′-bipyridine. The present methodology provides access to 2,2′:6′,2″-terpyridineruthenium(II) starting from 5,5″-bis(methoxymethoxy)-4,4″-bis(substituted ethynyl)-2,2′:6′,2″-terpyridines via one-pot cleavage the methoxymethyl (MOM) protecting group, cycloisomerization, and metal complexation in presence...