Unlocking Chiral Sulfinimidoyl Electrophiles: Asymmetric Synthesis of Sulfinamides Catalyzed by Anionic Stereogenic-at-Cobalt(III) Complexes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, etc., which have garnered increasing attention in modern pharmaceutical sciences. However, the aza-analog of electrophiles, asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent significant challenge sulfur stereochemistry. Herein, we exhibit anionic stereogenic-at-cobalt(III) complex-catalyzed synthesis chiral sulfinamides via iodide intermediates. Mechanistic investigations reveal that catalytic cycle is initiated by oxidative iodination, generating iodides. These active intermediates subsequently undergo enantiospecific nucleophilic substitution with water, affording diverse array enantioenriched sulfinamides. Notably, these promising antifungal activities against Sclerotinia sclerotiorum serve ideal platform molecules facilitating stereospecific transformation into various stereogenic aza-sulfur compounds.

Language: Английский

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Copper-Catalyzed Sulfur Alkylation of Sulfenamides with N-Sulfonylhydrazones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3906 - 3910

Published: April 29, 2024

Sulfilimines are valuable compounds in both organic synthesis and pharmaceuticals. In this study, we present a copper-catalyzed sulfur alkylation of sulfenamides with

Language: Английский

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Deep eutectic solvents as sustainable media for multicomponent sulfonylation: an efficient strategy to synthesize (hetero)aryl sulfones

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(3), P. 1387 - 1392

Published: Jan. 1, 2024

A green and sustainable multicomponent sulfonylation starting from boronic acids, K 2 S O 5 halides has been developed using a deep eutectic solvent (DES) as reaction medium.

Language: Английский

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Ligand-Enabled Copper-Catalyzed Ullmann-Type S–C Bond Formation to Access Sulfilimines

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

Published: Sept. 12, 2024

A copper-catalyzed Ullmann-type cross-coupling reaction of sulfenamides with aryl iodides is developed. The key to success the use a 2-methylnaphthalen-1-amine-derived amide ligand, which enables formation an S-C bond access functionalized sulfilimines in good excellent yields at room temperature. This method has advantages mild conditions, broad substrate scope, functional group compatibility, and high chemoselectivity. utility this protocol highlighted through late-stage modification drug-relevant molecules sulfilimine product derivatization.

Language: Английский

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The Catalytic Synthesis of Aza-Sulfur Functional Groups

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

Published: Sept. 26, 2024

Abstract Sulfur-containing compounds are found in myriad applications. Sulfones and sulfonamides the most common functional groups used medicinal agrochemical endeavours. Isosteres of these groups, for example, sulfoximines sulfonimidamides, emerging functionalities, they increasingly relevant patent literature. However, general, associated synthetic routes still have limitations, including use harsh reaction conditions highly reactive reagents. A variety catalytic reactions that employ a diverse range substrate classes been developed to address issues. This short review highlights recent syntheses aza-sulfur compounds, which we hope will open new directions discovery chemistry. 1 Introduction 2 Reactions N-Sulfinylamines 3 with Sulfenamides 4 Sulfinates 5 Sulfinamides 6 Other Aza-Sulfur Compounds 7 Conclusion

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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Synthesis of sulfonyl‐containing spiro[5,5]trienones from sodium metabisulfite

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(13), P. 3041 - 3045

Published: May 11, 2024

Abstract An efficient three‐component reaction of biaryl ynones, sodium metabisulfite and aryldiazonium tetrafluoroborates is developed. The occurs at room temperature without any additives, thus offering a sustainable approach to access sulfonyl‐containing spiro[5,5]trienones. This protocol features mild conditions, broad substrate scope high functional group compatibility, furnishing the target products in moderate good yields. Mechanistic studies indicate that undergoes 6‐ exo ‐ trig dearomative spirocyclization process which initated by an aryl radical with insertion sulfur dioxide.

Language: Английский

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From Conventional to Sustainable Catalytic Approaches for Heterocycles Synthesis

ChemSusChem, Journal Year: 2023, Volume and Issue: 17(8)

Published: Dec. 23, 2023

Abstract Synthesis of heterocyclic compounds is fundamental for all the research area in chemistry, from drug synthesis to material science. In this framework, catalysed synthetic methods are great interest effective reach such important building blocks. review, we will report on some selected examples last five years, major improvement field, focusing most conventional catalytic systems, as transition metals, organocatalysts, more sustainable ones photocatalysts, iodine‐catalysed reaction, electrochemical reactions and green innovative methods.

Language: Английский

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Iron-catalyzed Selective Construction of Indole Derivatives via Oxidative C(sp3)-H Functionalization of Indolin-2-ones

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(15), P. 3073 - 3079

Published: Jan. 1, 2024

We have developed a clean and efficient iron-catalyzed C(sp 3 )–H functionalization of indolin-2-ones for the chemodivergent synthesis value-added indole derivatives, including isatins, symmetrical non-symmetrical isoindigos.

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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