Iron-catalysed stereoselective NH transfer enables dynamic kinetic resolution of sulfoxides

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 8, 2025

Transition metal-catalysed asymmetric nitrene transfer provides a powerful means to access various bioactive N-containing compounds as single enantiomers. However, enantioselective NH that allows concise assembly of unprotected enantioenriched amines remains an enduring challenge. We report here iron-catalysed stereoselective imidation sulfoxide, which is integrated with photocatalytic racemisation enabling dynamic kinetic resolution (DKR) strategy for direct and synthesis NH-sulfoximines. This approach distinct from the existing methods by avoiding protecting group manipulations and/or use chiral substrates. Computational studies on reaction suggest involvement iron-aminyl radical intermediate, its sulfoxide proceeds through synchronous nucleophilic addition nitrogen center ligand-to-metal electron process form N–S bond. In addition, stereoselectivity primarily dictated difference in dispersion interactions transition states. Enantioselective Here, authors

Language: Английский

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Regioselective N-arylation of N-Acylsulfenamides Enabled by o-Quinone Diimides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

The functionalization of N-acylsulfenamides is a research focus in organosulfur chemistry, as the N-S array has unique properties and versatile applications. Although great progress been made S-functionalization, N-functionalization, especially N-arylation N-acylsulfenamides, rarely explored because lower nucleophilicity N-site. Herein, we report Brønsted acid-catalyzed regioselective reaction with o-quinone diimides. Under mild metal-free conditions, wide range N-arylated have prepared good yields excellent regioselectivity. ease gram-scale synthesis transformations into useful sulfonamides demonstrates their synthetic practicality.

Language: Английский

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Nucleophilic Substitution of Tertiary Sulfonamides: Construction of Sulfonate Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Under the combined action of trichloroisocyanuric acid (TCCA) and triflic (TfOH), tertiary sulfonamides are efficiently activated, leading to in situ generation electrophilic sulfonamide salts. These salts subsequently undergo nucleophilic substitution by alcohols, resulting formation sulfonate esters under mild conditions. Other advantages this method include absence transition-metal catalysts, broad substrate applicability, high functional-group tolerance.

Language: Английский

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Assembly of (hetero)aryl sulfilimines via copper-catalyzed enantioselective S-arylation of sulfenamides with (hetero)aryl Iodides

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 8, 2025

The (hetero)aryl sulfoximines are important structures for developing bioactive molecules, whose synthesis relies on oxidation of sulfilimines. However, asymmetric approaches assembling sulfilimines still rare. Here we show that combination CuI and NOBIN-derived amide ligands offers an effective catalytic system enantioselective coupling iodides with sulfenamides. A large number functional groups heterocycles tolerated under the conditions, providing a powerful approach diverse enantioenriched efficiency reaction is highly dependent electronic nature Both (hetero)aryl- some bulky alkyl-substituted sulfenamides give excellent enantioselectivities, while smaller alkyl substituents lead to formation moderate enantioselectivities. Density theory (DFT) calculations reveal proper steric repulsions in transition states intramolecular SNAr crucial achieving desirable enantioselectivity. (Hetero)aryl useful bioisosteres sulfones medicinal chemistry as they have improved aqueous solubility metabolic stability. Here, authors report via copper-catalysed

Language: Английский

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Assembly of (Hetero)aryl Sulfoximines via Copper-Catalyzed S-Arylation of Sulfinamides with (Hetero)aryl Halides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

The combination of CuI and 4-(dimethylamino)picolinamide offers an effective catalytic system for the successful coupling (hetero)aryl halides (I Br) with sulfinamides first time. A large number functional groups heterocycles were tolerated under conditions, providing a powerful approach diverse synthesis pharmaceutically important sulfoximines. efficiency reaction was highly dependent upon electronic nature substituents at amide part sulfinamides. By using enantioenriched as partners, proceeds in stereospecific manner to afford sulfoximines excellent enantioselectivity.

Language: Английский

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