Decarboxylative Radical Sulfilimination via Photoredox, Copper, and Brønsted Base Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 21, 2023

Sulfilimines, the aza-variants of sulfoxides, are key structural motifs in natural products, pharmaceuticals, and agrochemicals; sulfilimine synthesis is therefore important organic chemistry. However, methods for radical sulfilimination remain elusive, as a result, diversity currently available sulfilimines limited. Herein, we report first protocol decarboxylative reactions between sulfenamides N-hydroxyphthalimide esters primary, secondary, tertiary alkyl carboxylic acids, which were achieved via combination photoredox, copper, Brønsted base catalysis. This novel provided wide variety sulfilimines, addition to serving an efficient route S-alkyl/S-aryl homocysteine S-(4-methylphenyl) sulfoximine. Moreover, it could be used late-stage introduction group into structurally complex molecules, thereby avoiding need preserve labile organosulfur moieties through multistep synthetic sequences. A mechanism involving photocatalytic substrate transformation copper-mediated C(sp

Язык: Английский

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Synthesis of chiral sulfilimines by organocatalytic enantioselective sulfur alkylation of sulfenamides

Science Advances, Год журнала: 2024, Номер 10(37)

Опубликована: Сен. 13, 2024

Sulfilimines are versatile synthetic intermediates and important moieties in bioactive molecules. However, their applications drug discovery underexplored, efficient asymmetric methods highly desirable. Here, we report a transition metal–free pentanidium-catalyzed sulfur alkylation of sulfenamides with exclusive chemoselectivity over nitrogen high enantioselectivity. The reaction conditions were mild, wide range enantioenriched aryl alkyl sulfilimines obtained. utility practicability this robust protocol further demonstrated through gram-scale reactions late-stage functionalization drugs.

Язык: Английский

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A combined experimental and computational study of ligand-controlled Chan-Lam coupling of sulfenamides

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 4, 2024

Abstract The unique features of the sulfenamides’ S(II)-N bond lead to interesting stereochemical properties and significant industrial functions. Here we present a chemoselective Chan–Lam coupling sulfenamides prepare N -arylated sulfenamides. A tridentate pybox ligand governs chemoselectivity favoring C–N formation, overrides competitive C-S formation by preventing S,N-bis-chelation copper center. Cu(II)-derived resting state catalyst is captured UV-Vis spectra EPR technique, key intermediate confirmed isotope response using 15 N-labeled sulfenamide. computational mechanistic study reveals that -arylation both kinetically thermodynamically favorable, with deprotonation sulfenamide nitrogen atom occurring prior reductive elimination. origin ligand-controlled explored, interaction between substrate controlling energy S corresponding product distribution, in agreement studies kinetic results.

Язык: Английский

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1,2-Difunctionalization of Aryne with Sulfenamide and Organohalide: Mild and Metal-Free Access to S-(o-Halo)aryl Sulfilimine

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(12), С. 9043 - 9050

Опубликована: Июнь 6, 2024

A mild and metal-free approach has been developed for 1,2-difunctionalization of aryne using sulfenamides as a nucleophile halogen source (CX4) an electrophile to synthesize S-(o-halo)aryl sulfilimines. The late-stage functionalizations halide handles via Suzuki–Miyaura Buchwald–Hartwig reactions exhibit the synthetic utilities products. chemoselectivity, regioselectivity, rapidity, use economical CCl4 are advantages this protocol.

Язык: Английский

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Heterogeneous photocatalytic synthesis of sulfenamides with carbon doped potassium poly(heptazine imide) through effective electron delocalization

Green Chemistry, Год журнала: 2024, Номер 26(15), С. 8785 - 8793

Опубликована: Янв. 1, 2024

A ground-breaking light-driven strategy to synthesize sulfenamides using K-PHI-C doping is proposed. C-doping can extend optical absorption range near-infrared and create delocalized electronic density enhance the single electron transfer step.

Язык: Английский

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