Accessing Sulfonamides via Formal SO2 Insertion into C–N Bonds DOI Creative Commons
Myojeong Kim, Carys Obertone, Christopher B. Kelly

и другие.

Опубликована: Авг. 22, 2024

Functional group interconversions of abundant substructures that accommodate the often-complex molecular architectures seen in pharmaceuticals are particularly sought after by medicinal chemists as a means to enable both lead optimization and library diversification. Here, we report conceptually new strategy enables net SO 2 -insertion into C–N bond primary amines, enabling direct synthesis sulfonamides without pre-activation effectively inverting nitrogen’s properties (acidity, hydrogen bonding, etc.). The key realizing this overall transformation is implementation an anomeric amide dual-function reagent which serves cleave initial deliver nitrogen atom product incorporation. process tolerates wide array functionalities can be run automated fashion thus allowing libraries amines viable progenitors highly desirable sulfonamides. Mechanistic studies support isodiazene radical chain mechanism generates intermediate sulfinate reacts with forge S–N bond. As proof concept, our protocol was used conduct high-throughput diversification campaign, applied modification approved active pharmaceutical ingredients CO-to-SO “isosteric replacement” approach. Conceptually, successful translation originally developed for deletion insertion has important implications skeletal editing.

Язык: Английский

Visible-Light-Induced Decarboxylative Aminosulfonylation of (Hetero)aryl Carboxylic Oxime Esters DOI

Zhen Zhuang,

Yuting Sun, Yuanchen Zhong

и другие.

Organic Letters, Год журнала: 2024, Номер 26(3), С. 713 - 718

Опубликована: Янв. 12, 2024

Sulfonamides are important structures in pharmaceuticals, agrochemicals, and organocatalysts, yet the rapid benign synthesis of these compounds is still a great challenge. Herein we report photoinduced method for synthesizing sulfonamides from (hetero)aryl carboxylic acid oxime esters. This reaction proceeds via one-pot cascade radical–radical cross-coupling by energy-transfer-mediated photocatalysis. A wide substrate scope including substrates late-stage modification pharmaceutical molecular entities reveal its generality.

Язык: Английский

Процитировано

14
Multimodal Acridine Photocatalysis Enables Direct Access to Thiols from Carboxylic Acids and Elemental Sulfur DOI

Arka Porey,

Seth O. Fremin, Sachchida Nand

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6973 - 6980

Опубликована: Апрель 19, 2024

Development of photocatalytic systems that facilitate mechanistically divergent steps in complex catalytic manifolds by distinct activation modes can enable previously inaccessible synthetic transformations. However, multimodal remain understudied, impeding their implementation methodology. We report herein a access to thiols directly merges the structural diversity carboxylic acids with ready availability elemental sulfur without substrate preactivation. The transformation provides direct radical-mediated segue one most biologically important and synthetically versatile organosulfur functionalities, whose accessibility remains largely dominated two-electron-mediated processes based on toxic uneconomical reagents precursors. two-phase radical process is facilitated reactivity acridine photocatalysis enables both singlet excited state PCET-mediated decarboxylative carbon–sulfur bond formation unknown reductive disulfur cleavage photoinduced hydrogen atom transfer silane–triplet system. study points significant potential providing unexplored directions

Язык: Английский

Процитировано

11
Synthesis of S(IV)‐Stereogenic Chiral Thio‐Oxazolidinones via Palladium‐Catalyzed Asymmetric [3+2] Annulations DOI

Bao‐Cheng Wang,

Fang Hu,

Jiahui Bai

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Янв. 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.

Язык: Английский

Процитировано

10
Reductive sulfinylation by nucleophilic chain isomerization of sulfonylpyridinium DOI Creative Commons
Yifan Li, Weigang Zhang, Jeonguk Kweon

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 3, 2025

Язык: Английский

Процитировано

1
Dual Acridine/Decatungstate Photocatalysis for the Decarboxylative Radical Addition of Carboxylic Acids to Azomethines DOI

Zakhar M. Rubanov,

Vitalij V. Levin, Alexander D. Dilman

и другие.

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3174 - 3178

Опубликована: Апрель 8, 2024

A concept for the dual use of acridine and tetrabutylammonium decatungstate photocatalysts in reactions carboxylic acids is proposed. Imines generated situ from aldehydes p-methoxyaniline, as well other azomethines, were used radical acceptors. The role believed to facilitate turnover photocatalyst by means hydrogen atom transfer.

Язык: Английский

Процитировано

9
Iron-Catalyzed Photochemical Synthesis of Sulfinamides from Aliphatic Hydrocarbons and Sulfinylamines DOI

Guang-Da Xia,

Run Li, Long Zhang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(18), С. 3703 - 3708

Опубликована: Апрель 26, 2024

An iron-catalyzed photochemical sulfinamidation of hydrocarbons with

Язык: Английский

Процитировано

9
Acridine photocatalysis enables tricomponent direct decarboxylative amine construction DOI Creative Commons
Xianwei Sui, Hang T. Dang,

Arka Porey

и другие.

Chemical Science, Год журнала: 2024, Номер 15(25), С. 9582 - 9590

Опубликована: Янв. 1, 2024

Diverse amines and amino acids are now readily accessed from carboxylic acids, aldehydes, amine precursors in a direct decarboxylative reaction enabled by homogeneous triple catalytic system based on acridine photocatalysis.

Язык: Английский

Процитировано

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

Xiaowu Fang,

Minyan Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(26), С. 17587 - 17594

Опубликована: Июнь 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.

Язык: Английский

Процитировано

9
Photo-mediated radical relay oximinosulfonamidation of alkenes with N-nitrosamines triggered by DABSO DOI

Ji‐Wei Sang,

Hong Chen, Yu Zhang

и другие.

Green Chemistry, Год журнала: 2024, Номер 26(13), С. 7849 - 7856

Опубликована: Янв. 1, 2024

N -Nitrosamines represent a class of bifunctional nitrogen-radical precursors, but their application potential remains largely unexplored.

Язык: Английский

Процитировано

8
Electrochemical Conversions of Sulfenamides into Sulfonimidoyl- and Sulfondiimidoyl Fluorides DOI Creative Commons
Bin Zhao,

Diping Zeng,

Xinglei He

и другие.

JACS Au, Год журнала: 2025, Номер 5(5), С. 2359 - 2367

Опубликована: Апрель 29, 2025

The invention of versatile linkage agents provides the chemical basis for SuFEx chemistry. Sulfonimidoyl fluorides and sulfondiimidoyl are aza-isosteres sulfonyl with diverse reactivity through fine-tuning N-substituents. However, limited synthetic approaches impede their wide applications in Herein, we develop a straightforward electrochemical strategy sulfonimidoyl- sequential oxidations readily available sulfenamides via sulfinamide iminosulfinamide intermediates, respectively. previously rarely investigated (bis)-sulfondiimidoyl now easily accessible participate chemistry oxygen nitrogen nucleophiles, macrocyclization, polymerization.

Язык: Английский

Процитировано

1