Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1322 - 1345

Опубликована: Янв. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Язык: Английский

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Indane-Based Chiral Aryl Chalcogenide Catalysts: Development and Applications in Asymmetric Electrophilic Reactions

Accounts of Chemical Research, Год журнала: 2022, Номер 55(17), С. 2439 - 2453

Опубликована: Авг. 25, 2022

ConspectusAsymmetric electrophilic reactions provide an ideal method for the construction of chiral molecules by incorporating one or more functional groups into parent substrates under mild conditions. However, due to issues reactivities species and possible racemization intermediates as well restriction scaffolds catalysts, many limitations remain in this field, such narrow scopes electrophiles limited types nucleophiles reactions. To overcome synthesis diversified molecules, we developed a series indane-based amino aryl chalcogenide catalysts. These catalysts are easily prepared based on privileged indane scaffold. They can appropriate H-bonding effect varying protecting offer proper Lewis basicity steric hindrance adjusting different substituents motifs. features allow them meet requirements reactivity environment Notably, they have been successfully applied various asymmetric alkenes, alkynes, arenes, expanding field reactions.Using these realized enantioselective CF3S-lactonization olefinic carboxylic acids, CF3S-aminocyclization sulfonamides, desymmetrizing CF3S-carbocyclization gem-diaryl-tethered CF3S-oxycyclization N-allylamides, intermolecular trifluoromethylthiolating difunctionalization allylic C–H trifluoromethylthiolation trisubstituted formally CF3S-oxyfunctionalization aliphatic internal azidothiolation, oxythiolation, thioarylation N-allyl chlorocarbocyclization aryl-tethered diolefins, Friedel–Crafts-type chlorination anilides, dearomatization 1-naphthanilides. Additionally, carbothiolation alkynes construct enantiopure carbon chirality center-containing axially sulfide vinyl arenes aromatic halogenation produce P-chirogenic compounds be accomplished. In reactions, bifunctional binding mode is proposed catalytic cycles, which acid-derived anion-binding interaction might exist account high enantioselectivities reactions.In Account, demonstrate our achievements share thoughts catalyst design, understanding perspectives chalcogenide-catalyzed We hope that experience will promote design development other novel organocatalysts new challenging

Язык: Английский

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Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(7), С. 2943 - 2952

Опубликована: Фев. 10, 2022

Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation phenols has been achieved for first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination novel 3,3'-disubstituted BINOL-derived selenide catalyst an achiral sulfonic acid. Control experiments computational studies suggest that multiple noncovalent interactions between cocatalysts substrate, especially network hydrogen bond interactions, play crucial role in determining enantioselectivity reactivity.

Язык: Английский

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Direct Synthesis of Paracetamol via Site-Selective Electrochemical Ritter-type C–H Amination of Phenol

Organic Letters, Год журнала: 2022, Номер 24(12), С. 2310 - 2314

Опубликована: Март 21, 2022

The synthesis of paracetamol still relies on multistep protocols involving the utilization a stoichiometric amount oxidizing/reducing or other corrosive agents. Herein we report regioselective electrochemical Ritter-type reaction at C(sp2)–H unprotected phenol toward environmentally benign and direct paracetamol. proceeds under exogenous oxidant- catalyst-free conditions. protocol is scalable, can be deployed to variety phenols, offers sustainable alternative for

Язык: Английский

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Chalcogen bonding catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 586 - 605

Опубликована: Дек. 7, 2023

Catalysts play a major role in chemical synthesis, and catalysis is considered to be green economic process. Catalysis dominated by covalent interactions between the catalyst substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) are well established among catalysts, including asymmetric HB catalysts. Though halogen (XB) its version gaining admiration, chalcogen (ChB) budding stage. This tutorial review will focus on recently evolved emphasis given chiral molecules. Since successful enantioselective yet reported, this basics catalysis, chalcogenide rigidification transition states ChB, stabilization cations chalcogens, details unsuccessful enantioseparation racemic molecules using existence ChB biomolecules.

Язык: Английский

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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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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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Selenylation Chemistry Suitable for On‐Plate Parallel and On‐DNA Library Synthesis Enabling High‐Throughput Medicinal Chemistry

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(35)

Опубликована: Май 17, 2022

Abstract Click chemistry is a concept wherein modular synthesis used for rapid functional discovery. To this end, continuous discovery of clickable chemical transformations the pillar to support development field. This report details C3‐H selenylation indole that suitable on‐plate parallel and DNA‐encoded library ( Se DEL) via bioinspired LUMO activation strategy. reaction modular, robust highly site‐selective, it features simple mild system (catalyzed by nonmetallic B(C 6 F 5 ) 3 at room temperature), high yields excellent group compatibility. Using method, 1350 indole‐selenides was synthesized in an efficient practical manner, enabling identification ai as promising compound with nanomolar antiproliferative activity cancer cells situ phenotypic screening. These results indicate great potential new high‐throughput medicinal biology.

Язык: Английский

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Chiral sulfide and selenide catalysts for asymmetric halocyclizations and related reactions

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(16), С. 3263 - 3275

Опубликована: Янв. 1, 2023

Recent advances in chiral sulfide-catalyzed asymmetric halocyclizations are summarized.

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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