Assembly of (hetero)aryl sulfilimines via copper-catalyzed enantioselective S-arylation of sulfenamides with (hetero)aryl Iodides DOI Creative Commons
Mingchuang He,

Rongxing Zhang,

Tongkun Wang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 8, 2025

The (hetero)aryl sulfoximines are important structures for developing bioactive molecules, whose synthesis relies on oxidation of sulfilimines. However, asymmetric approaches assembling sulfilimines still rare. Here we show that combination CuI and NOBIN-derived amide ligands offers an effective catalytic system enantioselective coupling iodides with sulfenamides. A large number functional groups heterocycles tolerated under the conditions, providing a powerful approach diverse enantioenriched efficiency reaction is highly dependent electronic nature Both (hetero)aryl- some bulky alkyl-substituted sulfenamides give excellent enantioselectivities, while smaller alkyl substituents lead to formation moderate enantioselectivities. Density theory (DFT) calculations reveal proper steric repulsions in transition states intramolecular SNAr crucial achieving desirable enantioselectivity. (Hetero)aryl useful bioisosteres sulfones medicinal chemistry as they have improved aqueous solubility metabolic stability. Here, authors report via copper-catalysed

Language: Английский

Asymmetric synthesis of sulfoximines, sulfonimidoyl fluorides and sulfonimidamides enabled by an enantiopure bifunctional S(VI) reagent DOI
Shun Teng,

Zachary Shultz,

Chuan Shan

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(2), P. 183 - 192

Published: Jan. 18, 2024

Language: Английский

Citations

39
Enantioselective construction of stereogenic-at-sulfur(IV) centres via catalytic acyl transfer sulfinylation DOI
Tao Wei,

Han‐Le Wang,

Tian Yin

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1301 - 1311

Published: May 8, 2024

Language: Английский

Citations

20
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
Data Science-Enabled Palladium-Catalyzed Enantioselective Aryl-Carbonylation of Sulfonimidamides DOI
Lucy van Dijk, Brittany C. Haas, Ngiap‐Kie Lim

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(38), P. 20959 - 20967

Published: Sept. 1, 2023

New methods for the general asymmetric synthesis of sulfonimidamides are great interest due to their applications in medicinal chemistry, agrochemical discovery, and academic research. We report a palladium-catalyzed cross-coupling method enantioselective aryl-carbonylation sulfonimidamides. Using data science techniques, virtual library calculated bisphosphine ligand descriptors was used guide reaction optimization by effectively sampling catalyst chemical space. The optimized conditions identified using this approach provided desired product excellent yield enantioselectivity. As next step, science-driven strategy also explore diverse set aryl heteroaryl iodides, providing key information about scope limitations method. Furthermore, we tested range racemic compatibility coupling partner. developed offers efficient accessing enantioenriched sulfonimidamides, which should facilitate application industrial settings.

Language: Английский

Citations

36
Synthesis of Sulfilimines via Aryne and Cyclohexyne Intermediates DOI

Xianda Wu,

Minghong Chen, Fu‐Sheng He

et al.

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

Citations

32
Metal-Free Chemoselective S-Arylation of Sulfenamides To Access Sulfilimines DOI

Xianda Wu,

Yuqing Li, Minghong Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 9352 - 9359

Published: June 16, 2023

A novel and efficient S-arylation of sulfenamides with diaryliodonium salts for the synthesis sulfilimines is developed. The reaction proceeds smoothly under transition-metal-free air conditions, giving rapid access to in good excellent yields via selective S-C bond formation. This protocol scalable exhibits a broad substrate scope, functional group tolerance, chemoselectivity.

Language: Английский

Citations

26
Strain-promoted S-arylation and alkenylation of sulfinamides using arynes and cyclic alkynes DOI
Xi Zou,

Boming Shen,

Gaolin Li

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(3), P. 928 - 935

Published: Jan. 15, 2024

Language: Английский

Citations

11
Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines DOI
Yixiang Shi,

Yin Yuan,

Jianhui Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17580 - 17586

Published: June 20, 2024

The application of sulfinamides has been witnessed in medicinal and agrochemistry with employment asymmetric transformations. However, methods for their catalytic synthesis have rarely explored. Herein, the enantioselective addition aryl boroxines to sulfinylamines via Cu catalyst newly developed Xuphos ligand were reported. A series chiral can be readily accessed one step. This protocol enables stereospecific transformation sulfonimidoyl fluorides, sulfonimidamides, sulfonimidate esters. DFT calculations revealed reaction pathway, migratory insertion is enantio-determining noncovalent interaction between oxygen atom C-H bonds crucial enantioselectivity control.

Language: Английский

Citations

10
Synthesis of S(IV)‐Stereogenic Chiral Thio‐Oxazolidinones via Palladium‐Catalyzed Asymmetric [3+2] Annulations DOI

Bao‐Cheng Wang,

Fang Hu,

Jiahui Bai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 29, 2024

Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, drugs, materials. Compared with acyclic ones, the catalytic synthesis of thio-heterocycles has largely lagged behind due to lack efficient synthetic strategies. Here we establish first modular platform access thio-oxazolidinones via Pd-catalyzed [3+2] annulations vinylethylene carbonates sulfinylanilines. This protocol is featured by readily available starting materials, high enantio- diastereoselectivity. In particular, an unusual effect non-chiral supporting ligand diastereoselectivity was observed. Possible reaction mechanisms stereocontrol models were proposed.

Language: Английский

Citations

9
Asymmetric 2,3-Addition of Sulfinylamines with Arylboronic Acids Enabled by Nickel Catalysis DOI
Longlong Xi,

Xiaowu Fang,

Minyan Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17587 - 17594

Published: June 24, 2024

Sulfinamides have been widely used in organic synthesis, with research on their preparation spanning more than a century. Despite advancements catalytic methodologies, creating sulfur stereocenters within these molecules remains significant challenge. In this study, we present an effective and versatile method for synthesizing diverse range of S-chirogenic sulfinamides through asymmetric aryl addition to sulfinylamines. By utilizing nickel complex as catalyst, process exhibits impressive enantioselectivity can incorporate various arylboronic acids at the position. The resulting synthetic are stable highly adaptable, allowing conversion variety sulfur-containing compounds. Our study also incorporates detailed experimental computational studies elucidate reaction mechanism factors influencing enantioselectivity.

Language: Английский

Citations

8