Synthesis of Large Macrocycles with Chiral Sulfur Centers via Enantiospecific SuFEx and SuPhenEx Click Reactions DOI Creative Commons
Yang Chao, Muthusamy Subramaniam, Kayambu Namitharan

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15658 - 15665

Published: Oct. 30, 2023

Here we report the first asymmetric synthesis of large chiral macrocycles with sulfur atoms. Building on stereospecific SuFEx and SuPhenEx click chemistries, this approach utilizes disulfonimidoyl fluorides p-nitrophenolates─which are efficient building blocks two centers, diphenols to efficiently form novel S–O bonds. Characteristic results include enantiospecific one-step rings consisting 21–58 members characterization both enantiomers (R,R S,S) by e.g. X-ray crystallography.

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
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
Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis DOI

Yin Yuan,

Yidan Han,

Zhikun Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 27, 2024

Abstract Sulfur‐containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging persistent goal. Herein we report highly enantio‐ chemoselective cross–coupling sulfenamides with aryl diazonium salt construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide play crucial role achieving high reactivity selectivity. This approach provides general, modular divergent framework for quickly synthesizing chiral sulfoximines that are otherwise access. In addition, the origins chemoselectivity enantioselectivity were extensively investigated using density theory calculations.

Language: Английский

Citations

12
Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer DOI
Zhenzhong Liu, Hongli Wu,

H Huiqi Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Language: Английский

Citations

11
Enantioselective Chan–Lam S-arylation of sulfenamides DOI

Qingjin Liang,

Xinping Zhang, Madeline E. Rotella

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(9), P. 1010 - 1020

Published: Sept. 9, 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