Overcoming a Radical Polarity Mismatch in Strain‐Release Pentafluorosulfanylation of [1.1.0]Bicyclobutanes: An Entryway to Sulfone‐ and Carbonyl‐Containing SF₅‐Cyclobutanes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: Jan. 18, 2024

The first assortment of achiral pentafluorosulfanylated cyclobutanes (SF

Language: Английский

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BF₃-Catalyzed Intramolecular Fluorocarbamoylation of Alkynes via Halide Recycling

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11012 - 11018

Published: May 12, 2023

A BF3-catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion alkynes into strong C-F bonds through halide recycling mechanism. developed method provides access to 3-(fluoromethylene) oxindoles γ-lactams with excellent stereoselectivity, including fluorinated derivatives known protein kinase inhibitors. Experimental computational studies support stepwise mechanism for involving turnover-limiting cyclization step, followed by internal transfer from BF3-coordinated adduct. For methylene oxindoles, thermodynamically driven Z-E isomerization facilitated transition state aromatic character. In contrast, this stabilization not relevant γ-lactams, which results in higher barrier exclusive formation Z-isomer.

Language: Английский

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Regio‐ and Stereoselective Hydroelementation of SF₅‐Alkynes and Further Functionalizations.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 9, 2023

Herein is described a fully regio- and stereoselective hydroelementation reaction of SF5 -alkynes with N, O S-nucleophiles further functionalization the corresponding Z-(hetero)vinyl-SF5 intermediates, suitable platform to access α-SF5 ketones esters, β-SF5 amines alcohols under mild conditions. Experimental computational comparative studies between - CF3 have been performed highlight explain difference reactivity selectivity observed these two fluorinated motifs.

Language: Английский

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Expanding Radical Chloropentafluorosulfanylation of Alkynes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 365 - 369

Published: Jan. 2, 2024

The chloropentafluorosulfanylation of alkynes is a delicate but crucial operation for accessing SF5-alkynes that serve as substrates in numerous transformations. Dolbier's procedure using Et3B/O2 was the most efficient approach, while recent efforts make use other initiators and light activation. We found THF, single stimulus, sufficient to trigger reaction SF5Cl with alkynes. determined configuration Cl/SF5 products clarified structure side-products.

Language: Английский

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Three‐Component Reaction of Pentafluorosulfanyl Chloride, Alkenes and Diazo Compounds and Synthesis of Pentafluorosulfanylfurans

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 9, 2022

We report herein the three-component radical addition reaction of SF5 Cl, alkene and diazo compounds for selective formation α-alkyl-α-SF5 carbonyl compounds. The proceeded through first with compound followed by in situ generated carbon to alkene. synthetic useful α-allyl-α-SF5 were successfully prepared when allyl trimethylsilanes used as substrates. Furthermore, adducts formed from α-diazoacetophenones vinyl acetates converted into pentafluorosulfanylfurans. This transformation provided a practical efficeint method synthesis

Language: Английский

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Oxidative Fluorination of Heteroatoms Enabled by Trichloroisocyanuric Acid and Potassium Fluoride

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 17, 2022

Abstract In synthetic method development, the most rewarding path is seldom a straight line. While our initial entry into pentafluorosulfanyl (SF 5 ) chemistry did not go according to plan (due inaccessibility of reagents such as SF Cl at time), “detour” led us establish mild and inexpensive oxidative fluorination conditions that made aryl‐SF compound synthesis more accessible. The involved use potassium fluoride trichloroisocyanuric acid (TCICA)—a common swimming pool disinfectant—as opposed previously employed F 2 , XeF HF, . Thereafter, curiosity explore applications TCICA/KF general approach fluorinated Group 15, 16, 17 heteroatoms in organic scaffolds; this, turn, prompted SC‐XRD, VT‐NMR, computational, physical studies. Ultimately, it was discovered can be used synthesize Cl, enabling an unexpected way.

Language: Английский

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Recent advances in the chemistry and the application of SF5-compounds

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 9, 2024

Abstract This review article outlines the literature from 2022 to 2024 covering developments in SF5 chemistry. Recent synthetic methodologies of SF5-containing building blocks are reported. These methods include synthesis SF5Cl and its use pentafluorosulfanylation reactions oxidative fluorination reactions. Moreover, reactivity SF5-alkynes as versatile platform access new SF5-compounds is described. Finally, effects moiety highlighted according application different fields, such biological/medicinal chemistry, catalysis, material sciences. 1 Introduction 2 Access SF5-Containing Building Blocks 2.1 By Means 2.1.1 Generation 2.2 Oxidative Fluorination 2.3 SF5-Alkynes 2.4 Other Miscellaneous Aromatic Aliphatic SF5-Compounds 3 Applications 3.1 Medicinal Biological Chemistry 3.2 Material Science 3.3 Catalysis 4 Conclusion

Language: Английский

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Photo-induced hydroxypentafluorosulfanylation of alkenes with SF5Cl and oxygen gas and their further derivatization

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 9, 2024

Fluorinated or fluoroalkylated alcohols are common structural motifs in biologically active molecules, natural products, and pharmaceuticals. However, pentafluorosulfanyl (SF

Language: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

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Novel N(SCF₃)(CF₃)-amines: synthesis, scalability and stability

Chemical Science, Journal Year: 2023, Volume and Issue: 14(14), P. 3893 - 3898

Published: Jan. 1, 2023

We disclosed herein a straightforward strategy for the synthesis of unprecedented N-((trifluoromethyl)thio), N-(trifluoromethyl) amines using combination isothiocyanates with fluoride source and an electrophilic trifluoromethylthiolation reagent. More interestingly, scalability methodology has been demonstrated stability new motif studied.

Language: Английский

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