Atroposelective Synthesis of N‐Arylated Quinoids by Organocatalytic Tandem N‐Arylation/Oxidation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 12, 2022

Abstract Diarylamines and related scaffolds are ubiquitous atropisomeric chemotypes in biologically active natural products. However, the catalytic asymmetric synthesis of these axially chiral compounds remains largely unexplored. Herein, we report that a BINOL‐derived phosphoric acid (CPA) successfully catalyzed atroposelective coupling quinone esters anilines through direct C−N bond formation to afford N‐aryl atropisomers with an unprecedented intramolecular N−H−O hydrogen within six‐membered ring good yields enantioselectivities ester as both electrophile oxidant. A gram‐scale experiment demonstrated utility this synthetic protocol. Moreover, methodology provides platform for structurally diverse secondary amine by nucleophilic addition.

Language: Английский

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Catalytic Enantioselective Intermolecular Three-Component Sulfenylative Difunctionalizations of 1,3-Dienes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2715 - 2722

Published: Feb. 7, 2023

This work demonstrates regio- and enantioselective intermolecular three-component oxysulfenylations of 1,3-dienes with alcohols, phenols, acids, water as O-nucleophiles. These reactions were enabled by the cooperative catalysis chiral sulfide phosphoric acid. Various useful sulfur-containing allylic ethers, esters, alcohols readily obtained in moderate to excellent yields high enantioselectivities regioselectivities. protocol provides chemo-, regio-, together a broad scope good functional group compatibility.

Language: Английский

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Catalytic asymmetric synthesis of sulfur-containing atropisomers by C-S bond formations

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(12), P. 3331 - 3346

Published: Nov. 17, 2023

Language: Английский

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Synthetic Strategies to Control C–N Atropisomerism in Acyclic Amines and Amides

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2427 - 2438

Published: Feb. 21, 2023

Abstract Atropisomeric molecules are a privileged class of stereogenic material that have important applications in catalysis, materials science and medicines. To date, the majority work has been focused upon biaryl heterobiaryl scaffolds involving restricted rotation between pair cyclic fragments, but C–N atropisomeric based amines amides, where nitrogen atom is not part ring system, rapidly emerging as an molecules. This focus this Short Review, which begins by discussing factors influence configurational stability such provides historical background to their synthesis. followed detailed discussion state-of-the-art catalytic asymmetric strategies now available access C–Nacyclic atropisomers including carboxamides, sulfonamides, sulfinamides, phosphamides diarylamines. A variety different synthetic approaches discussed, kinetic resolution/desymmetrization, amination, C–H functionalization, N-functionalization, annulation. 1 Introduction 2 Atropisomerism Acyclic Amines Amides 3 Synthesis Directed Chiral Auxiliary 4 Atropselective 4.1 Kinetic Resolution Desymmetrization 4.2 Electrophilic Amination 4.3 Functionalization 4.4 N-Functionalization 4.5 Annulation 5 Conclusions Outlook

Language: Английский

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Lewis Base Catalyzed Selenofunctionalization of Alkynes with Acid‐Controlled Divergent Chemoselectivity^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(14), P. 1623 - 1629

Published: March 15, 2024

Comprehensive Summary Lewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time. Various selenium‐containing tetrasubstituted alkenes readily obtained in moderate to excellent yields with complete E / Z selectivities. As substrates 1‐ethynyl naphthol derivatives, linear produced via intermolecular oxygen nucleophilic attack absence additive; contrast, cyclic generated through intramolecular carbon capture addition acid.

Language: Английский

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Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation

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

Published: Nov. 15, 2024

Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report

Language: Английский

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Enantioselective Catalytic Synthesis of Inherently Chiral Calixarenes

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Since the introduction of concept inherent chirality by Böhmer, an important part research focused on asymmetric synthesis calixarene macrocycles. However, long synthetic procedures and tedious separation strategies hampered application this technology in many topics organic chemistry, including enantioselective molecular recognition catalysis. Very recently, a new generation catalytic methodologies has been reported, able to provide highly functionalized, inherently chiral calixarenes straightforward manner. In review, we will discuss these methods versatile properties such macrocycles that call for potential applications areas science.

Language: Английский

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Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols

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

Published: March 3, 2025

A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis a chiral sulfide and an achiral sulfonic acid. The designed synthesized catalyst selenylating reagent play crucial role in enhancing both enantioselectivity reactivity. This approach exhibits excellent regio-, chemo-, enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, aniline derivatives. Mechanistic studies reveal that combination acid not only facilitates formation catalytically active species, but also governs reaction. Meanwhile, density functional theory calculations disclose four hydrogen bond interactions π‧‧‧π interaction are responsible for observed enantioselectivity. Rearrangement reactions serve as steps syntheses biologically provide intellectual conceptual curiosities within broad field organic chemistry. Here, authors report allenols, catalysed Lewis base.

Language: Английский

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Iron-Catalyzed Thioarylation of Arenes Using Saccharin-Derived Reagents

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Biaryl sulfides are important scaffolds found in various natural products and pharmaceutically active compounds. One of the main approaches for synthesis this compound class involves substitution arenes using electrophilic thioaryl species. However, these methods generally require acidic activation electrophile, more forcing conditions, long reaction times. Here, we describe combination super Lewis acid iron(III) triflimide with saccharin-based thioarylation reagents rapid unsymmetrical biaryl under mild conditions. This approach was effective electron-deficient species that performed poorly previous methods, allowing efficient functionalization bioactive

Language: Английский

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Organocatalytic atroposelective synthesis of naphthoquinone thioglycosides from aryl-naphthoquinones and thiosugars

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(47), P. 7279 - 7282

Published: Jan. 1, 2023

In this study, we report an organocatalytic formal coupling strategy for aryl-naphthoquinones with thiosugars that provides straightforward access to the axially chiral naphthoquinone thioglycoside excellent stereoselectivity. Mechanistic studies revealed key role of H-bonding in stereochemical recognition. The reaction pathway involves atroposelective addition, followed by stereoretentive oxidation hydroquinone intermediate.

Language: Английский

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