Synthesis of Chiral Sulfilimines via Copper-Catalyzed Enantiospecific Arylation of Sulfenamides.

Chiral sulfilimines represent a type of chiral S(IV) compound that is versatile as pharmacophores and chiral building blocks for chiral S(VI) compounds. Herein, we report an efficient method of preparing chiral sulfilimines (up to 90% yield and up to 96% enantiomeric excess) from commercially available diaryliodonium salts and prochiral sulfenamides. The reaction was enlarged to the gram scale for the preparation of chiral sulfilimines and allowed for the derivatization of chiral sulfoximines and sulfondiimines with complete retention of stereochemistry.

• Publication year

  2025

• Venue

  Journal of Organic Chemistry

• Publication date

  2025-09-11

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/acs.joc.5c01081PMID 40935809
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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

  2025cited by this paper
• Assembly of (hetero)aryl sulfilimines via copper-catalyzed enantioselective S-arylation of sulfenamides with (hetero)aryl Iodides

  2025cited by this paper
• Dual Copper/Photoredox Catalysis for Radical-Mediated Arylation and Alkylation of Sulfenamides

  2025cited by this paper
• Sulfilimines from a Medicinal Chemist's Perspective: Physicochemical and in Vitro Parameters Relevant for Drug Discovery.

  2025cited by this paper
• Recent Advances in Asymmetric Synthesis of Chiral-at-Sulfur Sulfoximines

  2025cited by this paper
• Ligand-Enabled Copper-Catalyzed Ullmann-Type S-C Bond Formation to Access Sulfilimines.

  2024cited by this paper
• Photoredox-Catalyzed Difunctionalization of Alkenes with Sulfilimines.

  2024cited by this paper
• Enantioselective Chan–Lam S-arylation of sulfenamides

  2024cited by this paper
• Enantioselective S-Alkylation of Sulfenamides by Phase-Transfer Catalysis.

  2024cited by this paper
• Rh(II)-Catalyzed Enantioselective S-Alkylation of Sulfenamides with Acceptor-Acceptor Diazo Compounds Enables the Synthesis of Sulfoximines Displaying Diverse Functionality.

  2024cited by this paper
• The Modular Synthesis of Sulfondiimidoyl Fluorides and their Application to Sulfondiimidamide and Sulfondiimine Synthesis.

  2024cited by this paper
• Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer.

  2024cited by this paper
• Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis.

  2024cited by this paper
• Asymmetric S-Arylation of Sulfenamides to Access Axially Chiral Sulfilimines Enabled by Anionic Stereogenic-at-Cobalt(III) Complexes.

  2024cited by this paper
• Friedel-Crafts Reactivity with Sulfondiimidoyl Fluorides for the Synthesis of Heteroaryl Sulfondiimines.

  2024cited by this paper
• Synthesis of Aza‐S(VI) Fluorides and Primary Sulfonimidamides from Sulfinylamines

  2024cited by this paper
• Synthesis of chiral sulfilimines by organocatalytic enantioselective sulfur alkylation of sulfenamides

  2024cited by this paper
• Preparation of Sulfilimines by Sulfur-Alkylation of N-Acyl Sulfenamides with Alkyl Halides.

  2023cited by this paper
• Asymmetric Synthesis of Chiral Sulfimides through the O-Alkylation of Enantioenriched Sulfinamides and Addition of Carbon Nucleophiles.

  2023cited by this paper
• Synthesis of Sulfilimines via Selective S-C Bond Formation in Water.

  2023cited by this paper
• Synthesis of Sulfilimines via Multicomponent Reaction of Arynes, Sulfamides, and Thiosulfonates.

  2023cited by this paper
• Selective S-Arylation of Sulfenamides with Arynes: Access to Sulfilimines.

  2023cited by this paper
• Decarboxylative Radical Sulfilimination via Photoredox, Copper, and Brønsted Base Catalysis.

  2023cited by this paper
• Sulfondiimidamides as new functional groups for synthetic and medicinal chemistry

  2022cited by this paper
• Catalytic Enantioselective Sulfur Alkylation of Sulfenamides for the Asymmetric Synthesis of Sulfoximines.

  2022cited by this paper
• Biomolecule-Compatible Dehydrogenative Chan-Lam Coupling of Free Sulfilimines.

  2022cited by this paper
• [4+3]-Cycloaddition Reaction of Sulfilimines with Cyclobutenones: Access to Benzazepinones.

  2021cited by this paper
• Ruthenium-Catalyzed Asymmetric N-Acyl Nitrene Transfer Reaction: Imidation of Sulfide.

  2020cited by this paper
• Application of sulfoximines in medicinal chemistry from 2013 to 2020.

  2020cited by this paper
• Selective Synthesis of N-Cyano Sulfilimines by Dearomatizing Stable Thionium Ions

  2020cited by this paper
• Synthesis and Acaricidal- and Insecticidal-Activity Evaluation of Novel Oxazolines Containing Sulfiliminyl Moieties and Their Derivatives.

  2019cited by this paper
• Direct thioamination of arynes via reaction with sulfilimines and migratory N-arylation.

  2015cited by this paper
• Enantioselective Imidation of Sulfides via Enzyme-Catalyzed Intermolecular Nitrogen-Atom Transfer

  2014cited by this paper
• Insecticidal activities of chiral N-trifluoroacetyl sulfilimines as potential ryanodine receptor modulators.

  2014cited by this paper
• Rhodium-catalyzed stereoselective amination of thioethers with N-mesyloxycarbamates: DMAP and bis(DMAP)CH(2)Cl(2) as key additives.

  2014cited by this paper
• Enantioselective nitrene transfer to sulfides catalyzed by a chiral iron complex.

  2013cited by this paper
• A Sulfilimine Bond Identified in Collagen IV

  2009cited by this paper
• Stereoselective rhodium-catalyzed imination of sulfides.

  2008cited by this paper
• CATALYTIC ASYMMETRIC SULFIMIDATION

  1997cited by this paper
• Novel asymmetric catalytic synthesis of sulfimides

  1996cited by this paper
• The chemistry of sulfilimines

  1977cited by this paper

• Copper-Catalyzed Three-Component Sulfur-Stereogenic Sulfilimination of Conjugated and Cumulated Dienes

  2026cites this paper
• Enantioselective S-Alkylation of Sulfenamides With Copper-Catalyzed Amino-Radical-Transfer Deboronation.

  2026cites this paper
• β-Sulfinimidoyl Esters as Sulfenamide Anion Precursors for Accessing Aza-Sulfur Stereogenic Centers.

  2025cites this paper