Enantioselective Synthesis of Chiral Sulfonimidoyl Fluorides Facilitates Stereospecific SuFEx Click Chemistry DOI Open Access

He-sen Huang,

Yi Yuan, Wei Wang

et al.

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

Published: Nov. 5, 2024

Abstract Sulfur‐centered electrophilic ‘warheads’ have emerged as key components for chemical proteomic probes through sulfur‐exchange chemistry (SuFEx) with protein nucleophiles. Among these functional groups, sulfonimidoyl fluorides (SIFs) stand out their modifiable sites, tunable electrophilicities, and chiral sulfur‐center, presenting exciting possibilities new covalent probes. However, the synthetic access to SIFs has been a challenge, limiting exploration applications. In this study, we describe convenient route obtain from readily available sulfenamides via series of one‐pot tandem reactions high enantiomeric excess (ees). The resulting were further converted into diverse array S(VI) derivatives under mild conditions or in buffer solutions. Most significantly, specificity ligation experiments underscored critical role sulfur‐center chirality design screening more‐selective therapeutics.

Language: Английский

Enantioselective sulfur(VI) fluoride exchange reaction of iminosulfur oxydifluorides DOI
Zhiyuan Peng, Shoujun Sun, Meng‐Meng Zheng

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(3), P. 353 - 362

Published: Feb. 14, 2024

Language: Английский

Citations

23
Enantioselective sulfinylation of alcohols and amines by condensation with sulfinates DOI

Minghong Liao,

Yonggui Liu,

Hongyan Long

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(5), P. 1541 - 1552

Published: March 15, 2024

Language: Английский

Citations

20
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
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
Construction of Asymmetric C–S Bonds via an Electrochemical Catalysis DOI
Xiang Sun, Yan Zhang,

Tong Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1566 - 1572

Published: Feb. 16, 2024

Construction of asymmetric C–S bonds was realized via electrochemical catalysis in the presence a chiral nickel complex. The reaction can be carried out with excellent stereoselectivity and great functional group tolerance. corresponding products provide crucial precursors for some materials pharmaceutical drugs.

Language: Английский

Citations

8
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
Recent advances in catalytic asymmetric synthesis DOI Creative Commons

Ashna Garg,

Dominick Rendina,

Hersh Bendale

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: May 9, 2024

Asymmetric catalysis stands at the forefront of modern chemistry, serving as a cornerstone for efficient creation enantiopure chiral molecules characterized by their high selectivity. In this review, we delve into realm asymmetric catalytic reactions, which spans various methodologies, each contributing to broader landscape enantioselective synthesis molecules. Transition metals play central role catalysts wide range transformations with ligands such phosphines, N -heterocyclic carbenes (NHCs), etc., facilitating formation C-C and C-X bonds, enabling precise control over stereochemistry. Enantioselective photocatalytic reactions leverage power light driving force electrocatalysis has emerged sustainable approach, being both atom-efficient environmentally friendly, while offering versatile toolkit reductions oxidations. Biocatalysis relies on nature’s most catalysts, i.e., enzymes, provide exquisite selectivity, well tolerance diverse functional groups under mild conditions. Thus, enzymatic optical resolution, kinetic resolution dynamic have revolutionized production compounds. organocatalysis uses metal-free organocatalysts, consisting modular phosphorus, sulfur nitrogen components, remarkably transformations. Additionally, unlocking traditionally unreactive C-H bonds through selective functionalization expanded arsenal synthesis, atom-economical construction Incorporating flow chemistry been transformative, continuous systems reaction conditions, enhancing efficiency optimization. Researchers are increasingly adopting hybrid approaches that combine multiple strategies synergistically tackle complex synthetic challenges. This convergence holds great promise, propelling field forward in form. As these methodologies evolve complement one another, they push boundaries what can be accomplished leading discovery novel, highly may lead groundbreaking applications across industries.

Language: Английский

Citations

7
Organocatalytic skeletal reorganization for enantioselective synthesis of S-stereogenic sulfinamides DOI Creative Commons

Zanjiao Liu,

Siqiang Fang,

Haoze Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 22, 2024

Abstract The enantioselective synthesis of S -stereogenic sulfinamides has garnered considerable attention due to their structural and physicochemical properties. However, catalytic asymmetric still remains daunting challenges, impeding broad application in drug discovery development. Here, we present an approach for the through peptide-mimic phosphonium salt-catalyzed skeletal reorganization simple prochiral and/or racemic sulfoximines. This methodology allows facile access a diverse array substituted with excellent enantioselectivities, accommodating various substituent patterns desymmetrization or parallel kinetic resolution process. Mechanistic experiments, coupled density functional theory calculations, clarify stepwise pathway involving ring-opening ring-closing processes, step identified as crucial achieving stereoselective control. Given prevalence centers pharmaceuticals, anticipate that this protocol will enhance efficient precise relevant chiral molecules analogs, thereby contributing advancements discovery.

Language: Английский

Citations

7
Enantioselective Synthesis of Sulfinamidines via Asymmetric Nitrogen Transfer from N−H Oxaziridines to Sulfenamides DOI Creative Commons

Marc Fimm,

Fumito Saito

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

Published: May 15, 2024

Sulfinamidines are promising aza-S

Language: Английский

Citations

6