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

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1322 - 1345

Published: Jan. 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.

Language: Английский

---

Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(12), P. 4959 - 4964

Published: Jan. 22, 2020

The enantioselective construction of axially chiral compounds by electrophilic carbothiolation alkynes is disclosed for the first time. This transformation enabled use a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both arylthiolating trifluoromethylthiolating reagents are suitable this reaction. obtained products vinyl-aryl amino sulfides can be easily converted into biaryl sulfides, sulfoxides, amines, other valuable difunctionalized compounds.

Language: Английский

---

Advances in Asymmetric Di‐and Trifluoromethylthiolation, and Di‐ and Trifluoromethoxylation Reactions

Asian Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 8(5), P. 591 - 609

Published: Feb. 1, 2019

Abstract Methods to introduce fluorine atoms or fluoroalkyl groups are highly valuable the design and development of biologically active compounds. To date, majority fluorinated pharmaceuticals agrochemicals bear a atom CF 3 group at non‐stereogenic center. The methods for construction new, emerging motifs, in particular those combining heteroatom fluorocarbon moiety have witnessed tremendous advancement recent years; however, challenging problem is stereocontrol carbon center featuring such motifs. This review aims summarize asymmetric trifluoromethylthio‐ trifluoromethoxy compounds as well their difluoromethyl analogues. Both direct installation O−R f S−R (R =CF , 2 H) exploitation building blocks these detailed.

Language: Английский

---

Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(45), P. 19796 - 19819

Published: May 26, 2020

The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization alkenes initiated by electrophilic sulfenyl group transfer. addition sulfenium ions to results in generation chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible attack myriad nucleophiles stereospecific ring-opening event afford anti 1,2-sulfenofunctionalized products. practical application ion transfer been enabled advances field Lewis base catalysis. This Review will chronicle initial discovery and characterization followed determination their configurational stability challenges developing variants. Once framework reactivity established, critical analysis pioneering studies be presented. Finally, comprehensive discussion modern synthetic applications categorized around type nucleophile employed sulfenofunctionalization.

Language: Английский

---

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

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(17), P. 2439 - 2453

Published: Aug. 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

Language: Английский

---

A Toolbox of Reagents for Trifluoromethylthiolation: From Serendipitous Findings to Rational Design

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3359 - 3371

Published: Feb. 16, 2023

Two types of electrophilic trifluoromethylthiolating reagents were developed in the past 10 years our laboratory. The development first type reagent, trifluoromethanesulfenate I, which is highly reactive toward a variety nucleophiles, was based on an unexpected discovery initial design for reagent with hypervalent iodine skeleton. A structure–activity study disclosed that α-cumyl (reagent II) without iodo substituent equally effective. Subsequent derivatization let us develop bromodifluoromethanesulfenate III could be used preparation [18F]ArSCF3. To remediate low reactivity I Friedel–Crafts trifluoromethylthiolation electron-rich (hetero)arenes, we designed and prepared N-trifluoromethylthiosaccharin IV, exhibits broad various including arenes. comparison structure IV N-trifluoromethylthiophthalimide showed replacement one carbonyl group sulfonyl made much more electrophilic. Thus, both carbonyls two groups would further increase electrophilicity. Such rationale prompted to current most N-trifluoromethylthiodibenzenesulfonimide V, its higher than IV. We optically pure (1S)-(−)-N-trifluoromethylthio-2,10-camphorsultam VI, active trifluoromethylthio-substituted carbon stereogenic centers. Reagents I–VI now constitute powerful toolbox introduction trifluoromethylthio into target molecules.

Language: Английский

---

Chalcogen bonding catalysis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 586 - 605

Published: Dec. 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.

Language: Английский

---

Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13301 - 13309

Published: Oct. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Language: Английский

---

Copper‐Catalyzed Enantioselective C(sp³)−SCF₃ Coupling of Carbon‐Centered Benzyl Radicals with (Me₄N)SCF₃

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 26, 2024

Abstract In contrast with the well‐established C(sp 2 )−SCF 3 cross‐coupling to forge Ar−SCF bond, corresponding enantioselective coupling of readily available alkyl electrophiles chiral bond has remained largely unexplored. We herein disclose a copper‐catalyzed radical range secondary/tertiary benzyl radicals easily (Me 4 N)SCF reagent. The key success lies in utilization phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for simultaneous control reaction initiation enantioselectivity. This strategy can successfully realize two types asymmetric reactions, including enantioconvergent racemic halides three‐component 1,2‐carbotrifluoromethylthiolation arylated alkenes under mild conditions. It therefore provides highly flexible platform rapid assembly an array enantioenriched SCF ‐containing molecules interest organic synthesis medicinal chemistry.

Language: Английский

---

Three-Component Oxychalcogenation of Alkenes under Metal-Free Conditions: A Tetrabutylammonium Tribromide-Catalyzed System

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(5), P. 3054 - 3067

Published: Feb. 16, 2023

A three-component oxychalcogenation reaction, from alkenes, diselenides/thiophenols, and H2O/alcohols, has been realized herein. Tetrabutylammonium tribromide (TBATB) dimethylsulfoxide (DMSO) are utilized as the catalyst terminal oxidant, respectively, to enable this difunctionalization transformation. The metal-free reaction system shows good functional group compatibility, providing a unified practical approach access β-hydroxyl or β-alkoxy organochalcogenides.

Language: Английский

---