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

Yihua Fu,

Ruiying Xi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 2, 2024

Abstract 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.

Language: Английский

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 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.

Language: Английский

Citations

27
Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion DOI Creative Commons
Hao Guo, Jan‐Lukas Kirchhoff, Carsten Strohmann

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 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.

Language: Английский

Citations

18
Enantioselective cross-dehydrogenative coupling enabled by organocatalysis DOI
Quanbin Jiang, Jie Luo, Xiaodan Zhao

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(4), P. 1846 - 1875

Published: Jan. 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.

Language: Английский

Citations

6
Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy DOI Creative Commons

Wenpeng Ma,

Annika Schmidt, Carsten Strohmann

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 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.

Language: Английский

Citations

5
Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis DOI Creative Commons

Loïc Groslambert,

Patrick Pale, Victor Mamane

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 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

Language: Английский

Citations

5
Identification of C-C σ-hole⸱⸱⸱π interactions in the designed organometallic chloro-pyrazole-Pd(II) complex DOI
Debajyoti Saha, Asit Kumar Das, Mohammad Raish

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 141363 - 141363

Published: Jan. 1, 2025

Language: Английский

Citations

0
Cooperative Anion−π Catalysis with Chiral Molecular Cages toward Enantioselective Desymmetrization of Anhydrides DOI
Ming Yue, Na Luo, Xudong Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Exploiting novel noncovalent interactions for catalysis design represents a fascinating direction. For the flexible and relatively weak anion−π interactions, manipulation of two or more π-acidic surfaces cooperative activation is highly desirable. Here, we demonstrate strategy based on chiral molecular cages with V-shaped electron-deficient cavities synergic binding dicarbonyl electrophiles toward enantioselective desymmetrization transformation. The were readily synthesized by incorporation additional base sites in one step. efficiently catalyzed methanolytic series meso cyclic anhydrides nearly quantitative yields up to 94% ee. In contrast, non-cage analogues simple control catalysts showed sluggish conversion much lower enantioselectivity. Crystal structure, substrate studies, theoretical modeling consistently suggested essential role cage harnessing efficient excellent selectivity control.

Language: Английский

Citations

0
Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via SRN1 Process DOI Open Access

Yongliang Tu,

Xiang Li,

Bei‐Bei Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

Citations

0
Anion Recognition-Directed Supramolecular Catalysis with Functional Macrocycles and Molecular Cages DOI Creative Commons
Qi‐Qiang Wang

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 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.

Language: Английский

Citations

4
Computational Study of Hypervalent Chalcogen Bond Catalysis on the Hydroarylation of Styrene with Phenol: O-Activation vs π-Activation DOI
Chang Zhao, Ying Li, Wen‐Kai Chen

et al.

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

Published: Feb. 14, 2025

Chalcogen bond catalysis is gaining recognition in organocatalysis due to its environmental benignity and relatively low cost. The hypervalent selenium salts can drive the hydroarylation of styrene phenol, chalcogen···π has been proposed [Zhang, Q. Angew. Chem., Int. Ed. 2022, 61, e202208009]. In this work, phenol catalyzed by cyclic selenium-based catalysts investigated density functional theory (DFT) calculations, two activation modes are observed: one on (π-activation mode), other (O-activation mode). energy barriers via O-activation mode lower than those π-activation mode, our work may be more favorable. For for ortho-hydroarylation para-hydroarylation, which consistent with experimental observation that product major supports mode. Further investigation revealed stronger electrostatic interaction main factor leading compared para-hydroarylation. Moreover, substituent effect reactivity was investigated. This would provide a valuable perspective expanding applications chalcogen catalysis.

Language: Английский

Citations

0