Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Unlocking Chiral Sulfinimidoyl Electrophiles: Asymmetric Synthesis of Sulfinamides Catalyzed by Anionic Stereogenic-at-Cobalt(III) Complexes DOI
Hua‐Jie Jiang, Fang Wei, Xinran Chen

et al.

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

Citations

3
Mechanochemical syntheses of N-acyl sulfinamidines via iron-nitrenoids and their conversions to sulfur(VI) derivatives DOI Creative Commons

Shulei Pan,

Peng Wu, Yijie Hu

et al.

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

Published: April 1, 2025

Language: Английский

Citations

0
2‐Methylimidazole‐1‐(N‐tert‐octyl)sulfonimidoyl Fluoride: A Bench‐Stable Alternative to SOF4 as Precursor to N,O‐Substituted S(VI) Compounds DOI Creative Commons
Natassa Lional, Fedor M. Miloserdov, Han Zuilhof

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 10, 2024

S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF

Language: Английский

Citations

2
Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Citations

2
2‐Methylimidazole‐1‐(N‐tert‐octyl)sulfonimidoyl Fluoride: A Bench‐Stable Alternative to SOF4 as Precursor to N,O‐Substituted S(VI) Compounds DOI Creative Commons
Natassa Lional, Fedor M. Miloserdov, Han Zuilhof

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(36)

Published: June 10, 2024

Abstract S(VI) compounds with multiple N or O substituents are often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF 4 gas. Safety issues inaccessibility of strongly hamper developments these organic compounds. Here we describe synthesis applications 2‐methyl im idazole‐1‐( ‐ tert ‐octyl) s ulfonimidoyl f luoride (ImSF), a novel bench‐stable analogue . ImSF is synthesized gram scale via double fluorination t ‐OctNSO. We show can undergo substitution reactions phenols amines, which lead sulfurimidates sulfuramidimidates, respectively, intrinsically chiral analogous medicinally relevant sulfates sulfamates in an S=O moiety replaced by S=NR unit. Finally demonstrate that substitutions occur enantiospecifically, providing first entry sulfuramidimidates.

Language: Английский

Citations

1
Synthesis of Aza‐S(VI) Fluorides and Primary Sulfonimidamides from Sulfinylamines DOI Creative Commons
Michael Andresini,

Laura Marraffa,

Defne Şerbetçi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

Abstract Aza‐S(VI) fluorides are crucial compounds in the synthesis of various S(VI) derivatives, which find broad applications drug discovery. However, sulfonimidoyl and sulfondiimidoyl have been relatively underexplored, often requiring lengthy reaction sequences and/or use hazardous gaseous reagents. In this study, we present a rapid one‐pot method for producing from sulfinylamines via nucleophilic addition/electrophilic fluorination sequence. Similarly, can be synthesized using same sequence, preceded by formation unsymmetrical sulfurdiimides readily generated situ sulfinylamines. Whereas isolation was not feasible, they could efficiently converted into primary sulfonimidamides base hydrolysis process. Furthermore, explored reactivity aza‐S(VI) with nucleophiles, demonstrating versatile synthetic platform compounds.

Language: Английский

Citations

0
Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Citations

0