Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Язык: Английский

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

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

Опубликована: Март 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.

Язык: Английский

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Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 20, 2023

Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult-to-access glycosidic chemical space. C-Glycosylation, particular, has gained flurry of recent attention. However, most reported methods are restricted to the relatively facile access α-C-glycosides. Herein, we disclose β-stereoselective glycosylation indoles by employing phosphonoselenide catalyst. The robustness this protocol exemplified its amenability for reaction at both indolyl C- and N- reactivity sites. In contrast previous reports, which chalcogens were solely involved Lewis acidic activation, our mechanistic investigation unraveled that often neglected flanking aromatic substituents phosphonoselenides can substantially contribute catalysis engaging π-interactions. Computations NMR spectroscopy indicated chalcogenic components catalyst be collectively exploited foster conformational distortion glycal away from usual half-chair boat conformation, liberates convex β-face nucleophilic attack.

Язык: Английский

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Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Green Chemistry, Год журнала: 2024, Номер 26(4), С. 1846 - 1875

Опубликована: Янв. 1, 2024

Organocatalytic enantioselective cross-dehydrogenative coupling reaction provides a great opportunity for the synthesis of highly enantioenriched molecules. In this review, recent progress in field is summarized.

Язык: Английский

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Amphoteric chalcogen-bonding and halogen-bonding rotaxanes for anion or cation recognition

Nature Chemistry, Год журнала: 2025, Номер 17(3), С. 373 - 381

Опубликована: Фев. 20, 2025

Язык: Английский

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Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via S_RN1 Process

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Comprehensive Summary Cross‐coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB address these challenges enable very simple photoinduced cross‐electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role in facilitating single electron transfer processes, thereby enabling generation thiolates/selenolates from stable electrophiles α ‐aminoalkyl radicals, which possess capability abstract halogen atoms iodides. Moreover, provided support for radical nucleophilic substitution mechanism.

Язык: Английский

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Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Апрель 30, 2024

Abstract The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility phosphonochalcogenide (PCH) catalyst facilitate into challenging, but biologically interesting 7‐membered ring α,α’‐ C ‐disubstituted oxepane core through an α‐selective strain‐release ‐glycosylation. Methodically, this strategy represents switch from more common entropically less desired macrocyclizations thermodynamically favored ring‐expansion approach. In light general lack stereoselective methods ‐septanosides, remarkable palette silyl‐based nucleophiles can be reliably employed in our method. This include broad variety useful synthons, easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that mechanistic shift towards intramolecular aglycone transposition involving pentacoordinate silicon intermediate is likely responsible steering stereoselectivity.

Язык: Английский

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Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis

Chemistry - A European Journal, Год журнала: 2024, Номер 30(43)

Опубликована: Май 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Язык: Английский

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Anion Recognition-Directed Supramolecular Catalysis with Functional Macrocycles and Molecular Cages

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Окт. 25, 2024

ConspectusThe development of supramolecular chemistry has provided a variety host molecules and noncovalent tools for boosting catalytic processes, stimulating the emergence advance catalysis, among which macrocyclic cage-like compounds have attracted great attention due to their possession an enzyme-mimetic cavity recognition ability. While privileged scaffolds such as crown ethers, cyclodextrins, cucurbiturils, calixarenes, metal-coordinated cages been widely used, skeletons usually do not contain directional binding site; activation mainly rely on cation-associated interactions or hydrophobic effects. In this context, recent anion drawn our developing recognition-directed approach by using tailor-made functionalized macrocycles cages. Anions are important existing species in both biological chemical systems play role regulating structure function enzymes. We envisioned that taking advantage anions, including rich variety, diverse geometry, multiple interaction sites, sophisticated cooperation can be manipulated confined directing efficient selective catalysis.Following concept, we initiated study introducing typical thiourea H-bonding groups design synthesize series bis-thiourea macrocycles, especially chiral incorporating linkers. Taking obtained strong, cooperative binding, macrocycle-enabled counteranion trapping strategy was developed, afforded greatly enhanced efficiency excellent stereocontrol acid-catalyzing reactions. Furthermore, inspired sulfate-induced dimerization assembly, built substrate-induced assembly system, enabling induced-fit network enantioselective catalysis. addition, recognition-driven chirality gearing with more trithiourea cage revealed, could provide basis implementing anion-triggered allosteric catalysis within induced helical space. Not limited hydrogen bonding, emerging anion-π were largely exploited. A triazine-based prism containing three V-shaped electron-deficient π-cavities constructed, properties studied. Based established driving highly paved way push toward practical useful catalyst design.These results demonstrated anion-recognition direction serve powerful, versatile It is feasible only employing exogenous anions (e.g., counteranion) handle but also regulation anionic active intermediates/transition states, from use conventional recognition.

Язык: Английский

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Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 2, 2024

The efficient construction of chalcogen-atom-based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three-component or four-component reaction, through Se-S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti-inflammatory toward IL-1β low cytotoxicity.

Язык: Английский

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