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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Synthesis of Sulfilimines via Aryne and Cyclohexyne Intermediates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(27), P. 5157 - 5161

Published: July 5, 2023

An efficient and metal-free approach for the synthesis of sulfilimines from sulfenamides with aryne cyclohexyne precursors has been developed. The reaction proceeds through unusual S–C bond formation, which offers a novel practical entry to access wide range in moderate good yields excellent chemoselectivity. Moreover, this protocol is amenable gram-scale applicable transformation products into useful sulfoximines.

Language: Английский

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Azasulfur(iv) derivatives of sulfite and sulfinate esters by formal S–S bond insertion of dichloramines

Chemical Science, Journal Year: 2024, Volume and Issue: 15(14), P. 5333 - 5339

Published: Jan. 1, 2024

Starting from N , -dichloramines and S 8 or disulfides, azasulfur( iv ) chlorides are prepared, which easily derivatised by esterification amidation. The resulting products can be converted to a variety of complex sulfur( vi compounds.

Language: 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, Journal Year: 2024, Volume and Issue: 89(12), P. 9043 - 9050

Published: June 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.

Language: Английский

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Hypervalent Iodine Mediated Synthesis of Sulfinamidines from Sulfenamides

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(16), P. 11728 - 11734

Published: July 28, 2023

In this study, we present a novel, efficient method for the oxidative amination of sulfenamides using diacetoxyiodobenzene (PhI(OAc)2) and amines under basic conditions. This innovative technique streamlines synthesis sulfinamidines mild, metal-free conditions, achieving outstanding yields up to 99%. Furthermore, propose possible pathways that elucidate observed molecular sequence events in reaction. cutting-edge approach not only advances valuable sulfinamidine compounds but also expands synthetic toolbox available chemists, paving way future discoveries organic potential applications medicinal chemistry.

Language: Английский

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Selective S-Arylation of Sulfenamides with Arynes: Access to Sulfilimines

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7192 - 7197

Published: Sept. 21, 2023

Sulfilimines, the aza analogues of sulfoxides, are increasing interest in medicinal and agrochemical research programs. However, development efficient routes for their synthesis has remained relatively unexplored. In this study, we report a transition metal-free, selective S-arylation reaction between sulfenamides arynes, enabling facile preparation structurally diverse sulfilimines under mild redox-neutral conditions good yields. The application value our method was further demonstrated by scale-up synthesis, downstream derivatization, robustness screen.

Language: Английский

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Enantioselective Synthesis of Sulfinamidines via Asymmetric Nitrogen Transfer from N−H Oxaziridines to Sulfenamides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: May 15, 2024

Sulfinamidines are promising aza-S

Language: Английский

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Copper-Catalyzed Aerobic S-Amination of Sulfenamides for the Synthesis of Sulfinamidines

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(23), P. 16116 - 16121

Published: Nov. 20, 2023

Herein, we present a copper-catalyzed oxidative amination of sulfenamides for the synthesis sulfinamidines. By employment air as terminal oxidant, diverse array secondary and primary amines can be efficiently transformed into their corresponding products. This method is well-suited last-stage functionalization, underlying mechanism has been investigated. The transformation characterized by exceptional chemoselectivity, mild conditions, facile operation, broad substrate compatibility, which have significant implications fields pharmaceuticals organic synthesis.

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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Synthesis of N‐Acylsulfenamides from (Hetero)Aryl Iodides and Boronic Acids by One‐Pot Sulfur‐Arylation and Dealkylation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 28, 2023

Abstract A general one‐pot approach to diverse N ‐acylsulfenamides from a common S ‐phenethylsulfenamide starting material is reported. This was demonstrated by C−S bond formation utilizing commercially abundant (hetero)aryl iodides and boronic acids provide sulfilimine intermediates that undergo thermal elimination of styrene. In contrast, all prior approaches rely on thiol inputs introduce sulfenamide ‐substituents. broad scope reaction including for approved drugs drug precursors with dense display functionality. Several different types sulfur functionalization were performed derived complex precursor the blockbuster anticoagulant apixaban, highlighting utility this introduction high oxidation state groups in bioactive compounds. Mechanistic studies established key styrene step proceeds concerted does not require reagents or catalysts, therefore, should be applicable synthesis electrophiles conditions formation.

Language: Английский

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