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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Cu-Catalyzed Enantioselective S-Arylation of Sulfenamides Enabled by Confined Ligands

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

Published: March 20, 2025

Chiral sulfilimines, aza analogues of sulfoxides, are essential in natural products and pharmaceuticals, highlighting the importance their synthesis asymmetric catalysis. However, efficient approaches for synthesizing chiral diaryl sulfilimines still rare challenging, particularly those with two sterically similar aryl groups. Herein, we present a mild protocol generating diverse enantioenriched alkyl via copper-catalyzed enantioselective S-arylation N-acyl sulfenamides diaryliodonium salts. A bulky PyBox ligand is crucial stereocontrol, delivering various up to 95% ee (51 examples).

Language: Английский

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Mechanochemical syntheses of N-acyl sulfinamidines via iron-nitrenoids and their conversions to sulfur(VI) derivatives

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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Synthesis of Sulfinamidines via Iron-Catalyzed Nitrene Transfer Reaction with Sulfenamides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 18, 2024

An iron-catalyzed nitrene transfer reaction for the rapid synthesis of sulfinamidines from readily available sulfenamides is reported. This method features mild conditions, short times, and a broad substrate scope, allowing preparation variety in good to excellent yields. The synthetic utility sulfinamidine products was further demonstrated through their conversion other valuable sulfur(VI) compounds, such as sulfondiimidoyl fluorides, sulfinamidiate esters, sulfonimidamides. Preliminary efforts development an asymmetric variant showed moderate enantioselectivity.

Language: Английский

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Copper-catalyzed S-vinylation of sulfenamides for the synthesis of α,β-unsaturated sulfilimines

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: unknown, P. 102304 - 102304

Published: Nov. 1, 2024

Language: Английский

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Synthesis of Sulfenamides via Photoredox N–S Coupling of Dialkyl Azodicarboxylates and Thiols

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 27, 2024

We herein report a photoredox N–S coupling reaction between dialkyl azodicarboxylates and thiols to access sulfenamide scaffolds. This proceeds under mild, green, operationally simple conditions, offering broad scope of sulfenamides with high yields excellent atom efficiency. Mechanistic investigations revealed this followed photoinitiated radical pathway in which iodide plays crucial role as both initiator single-electron reductant.

Language: Английский

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