Rh(III)-Catalyzed Atroposelective C–H Selenylation of 1-Aryl Isoquinolines

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 6009 - 6015

Опубликована: Апрель 5, 2024

Rhodium(III)-catalyzed atroposelective C–H selenylation of 1-aryl isoquinolines has been achieved. The direct reaction between and 2-(phenylselanyl)isoindoline-1,3-dione in the presence chiral SCpRh(III) complex afforded a series axially isoquinoline selenides up to 95% yield 96% ee. features mild conditions broad substrate scope. DFT calculations revealed that C–Se bond formation step proceeds through formal SN2 pathway.

Язык: Английский

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Recent progress in the organoselenium-catalyzed difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Язык: Английский

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Atroposelective Electrophilic Sulfenylation ofN‐Aryl Aminoquinone Derivatives Catalyzed by Chiral SPINOL‐Derived Sulfide

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 30, 2022

Atroposelective electrophilic sulfenylation of N-aryl aminoquinone derivatives has been achieved for the first time. This transformation is enabled by a new chiral 6,6'-disubstituted SPINOL-derived sulfide catalyst, which was synthesized and then successfully explored catalyzing enantioselective reactions. Various axially sulfur-containing diarylamine were readily obtained in moderate to excellent yields with enantioselectivities. A class relatively flexible stereogenic C-N axes easily constructed. The experimental results computational study suggested that an intramolecular N-H⋅⋅⋅S hydrogen bond important stability axis, consistent our hypothesis. Density functional theory calculations revealed origin atroposelectivity underscored importance catalyst rigidity this reaction.

Язык: Английский

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Electrophilic Sulfur Reagent Design Enables Directed syn-Carbosulfenylation of Unactivated Alkenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7189 - 7197

Опубликована: Апрель 18, 2022

A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored electrophiles. The key development this transformation identification a modular N-alkyl-N-(arylsulfenyl)arenesulfonamide family sulfur Tuning electronic steric properties leaving group in these reagents controls pathway selectivity, favoring three-component coupling suppressing side reactions, as examined computational studies. unique syn-stereoselectivity differs from traditional electrophilic sulfenyl transfer processes involving thiiranium ion intermediate arises directed arylnickel(I) migratory insertion mechanism, elucidated through reaction kinetics control experiments. Reactivity regioselectivity are facilitated by collection monodentate, weakly coordinating native directing groups, including sulfonamides, alcohols, amines, amides, azaheterocycles.

Язык: Английский

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Atroposelective Sulfenylation of Biaryl Anilines Catalyzed by Chiral SPINOL-Derived Selenide

Organic Letters, Год журнала: 2023, Номер 25(19), С. 3445 - 3450

Опубликована: Май 11, 2023

The atroposelective electrophilic sulfenylation of biaryl anilines has been realized for the first time. reaction is enabled by a new chiral 6,6'-dianisole substituted SPINOL-derived selenide. A variety axially sulfur-containing aniline compounds were obtained in moderate to excellent yields with enantioselectivities. experimental results suggest that catalyst rigidity important high atroposelectivity.

Язык: Английский

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

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 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

Язык: Английский

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Chiral Selenide-Catalyzed, Highly Regio- and Enantioselective Intermolecular Thioarylation of Alkenes with Phenols

ACS Catalysis, Год журнала: 2021, Номер 11(6), С. 3755 - 3761

Опубликована: Март 10, 2021

Enantioselective electrophilic three-component thioarylation of alkenes by chiral selenide catalysis with free phenols as arylating sources is disclosed. A variety were achieved in high regio-, enantio-, and diastereoselectivities. Mechanistic studies revealed that this transformation went through carbon nucleophilic attack to give the products rather than process intramolecular rearrangement phenolic ether intermediates. The application organocatalytic method alkylation methoxy-substituted benzenes elucidated its generality.

Язык: Английский

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Alkylation Reactions with Alkylsulfonium Salts

Synthesis, Год журнала: 2021, Номер 54(06), С. 1478 - 1502

Опубликована: Окт. 25, 2021

Abstract The application of alkylsulfonium salts as alkyl-transfer reagents in organic synthesis has reemerged over the past few years. Numerous heteroatom- and carbon-centered nucleophiles, alkenes, arenes, alkynes, organometallic reagents, others are readily alkylated by under mild conditions. reactions feature convenience, high efficiency, accessible structurally diversified alkylation good functional group tolerance, a wide range substrate types, allowing facile various useful molecules from commercially available building blocks. This review summarizes using either isolated or situ formed via nucleophilic substitution, transition-metal-catalyzed reactions, photoredox processes. 1 Introduction 2 General Methods for Synthesis Alkylsulfonium Salts 3 Electrophilic Alkylation Using 4 Transition-Metal-Catalyzed 5 Photoredox-Catalyzed 6 Conclusion

Язык: Английский

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Chiral Lewis Base Catalyzed Enantioselective Selenocyclization of 1,1-Disubstituted Alkenes: Asymmetric Synthesis of Selenium-Containing 4H-3,1-Benzoxazines

Organic Letters, Год журнала: 2022, Номер 24(22), С. 4093 - 4098

Опубликована: Июнь 1, 2022

An enantioselective selenocyclization of 1,1-disubstituted alkenes was achieved for the first time, which is enabled by a novel combination chiral BINAM-derived sulfide and an achiral Lewis acid. Various selenium-containing 4H-3,1-benzoxazines, are widely present in range medicinally relevant molecules, were readily obtained moderate to good yields excellent enantioselectivities. A series tetrasubstituted carbon stereocenters facilely constructed.

Язык: Английский

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Recent Developments in Selenylation and Thiolation of Alkenes via Three‐component Reactions

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(14), С. 2310 - 2331

Опубликована: Июнь 24, 2023

Abstract Alkenes are valuable feedstocks in organic synthesis. Selenium or sulfur‐containing coumpounds with a neighboring functional group can be easily prepared by direct difunctionalization of alkenes via three‐component reactions. It will reduce the number steps and waste generation, form complicated molecules from simple starting materials. Herein, recent developments (2013–2022) have been summarized two categories: (1) selenylation seleniranium intermediates Se‐centered radicals; (2) thiolation more diverse mechanisms products Reactions electron‐rich arenes, alcohols, water, acids, NaN 3 , amines, KSCN, sulfamides, TMSNCS, TMSN Et N ⋅ 3HF, SOCl 2 HCl, NFSI, t BuONO, pyridinium salts, BuOOH, ArN BF 4 CO CO, O CF SO Cl, R P(O)−H, (RO) P(O)SH, P(O)OH et al discussed. We hope this review do help for future research area.

Язык: Английский

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