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

The Matere Bond DOI Creative Commons
Rosa M. Gomila, Antonio Frontera

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This article explores matere bonds, supported by theoretical and computational studies. These σ-hole interactions with group 7 elements (Mn, Tc, Re) are key in crystal engineering, catalysis, biological systems.

Language: Английский

Citations

6
Triethoxysilane-Catalyzed Single and Sequential Regioselective Hydroboration of Terminal Alkynes: Sustainable Access to E-Alkenylboronate and Alkyl Gem-Diboronate Esters by Non-Covalent Interactions DOI
Harleen Kaur,

Himani Ahuja,

Rebeca Arévalo

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 976 - 981

Published: Jan. 1, 2025

Triethoxysilane was found to be an efficient catalyst for the synthesis of E-alkenyl- and alkyl-di-boronate esters by single sequential hydroboration terminal alkynes, respectively, with pinacolborane. Mechanistic studies support that formation diboronate proceeds a double pathway steric electronic profile at Si being key enabling second step. Weak non-covalent interactions involving C≡C or C═C bonds in alkynes alkenylboronate have been identified as responsible substrate activation toward addition HBPin.

Language: Английский

Citations

1
Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters DOI
Alexandra A. Sysoeva, Yana V. Safinskaya, Mikhail V. Il’in

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Language: Английский

Citations

1
From covalent to noncovalent: The role of metals in activating ligand sites toward noncovalent interactions (NCIs) DOI
Nadezhda A. Bokach, Vadim Yu. Kukushkin

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 529, P. 216440 - 216440

Published: Jan. 15, 2025

Language: Английский

Citations

1
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

6
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

6
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 International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 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.

Language: Английский

Citations

6
Pnictogen‐Bonding Enzymes DOI Creative Commons
Giacomo Renno, Dongping Chen, Qingxia Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 5, 2024

Abstract The objective of this study was to create artificial enzymes that capitalize on pnictogen bonding, a σ‐hole interaction is essentially absent in biocatalysis. For purpose, stibine catalysts were equipped with biotin derivative and combined streptavidin mutants identify an efficient transfer hydrogenation catalyst for the reduction fluorogenic quinoline substrate. Increased catalytic activity from wild‐type best coincides depth σ hole Sb(V) center, emergence saturation kinetic behavior. Michaelis–Menten analysis reveals transition‐state recognition low micromolar range, more than three orders magnitude stronger millimolar substrate recognition. Carboxylates preferred by contribute hydrogen‐bonded ion pairing anion‐π interactions emerging pyridinium product. challenging stereoselectivity aqueous systems further emphasizes compatibility bonding higher order catalysis.

Language: Английский

Citations

5
Influence of Noncovalent Interaction on the Nucleophilicity and Electrophilicity of Metal Centers in [MII(S2CNEt2)2] (M = Ni, Pd, Pt) DOI
Zixuan Shen, Xiaoyan Li, Yanli Zeng

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

A systematic theoretical study was performed on the electrophilic and nucleophilic properties of Group 10 square-planar metal compounds [M

Language: Английский

Citations

3
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