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

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

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Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

Degradable chalcogenide polyesters, e.g., polythioesters (PTEs), typically exhibit improved thermal, mechanical, and optical properties. Anionic ring-opening polymerization (ROP) of thionolactones, an intrinsically promising yet underexplored approach to accessing PTEs, however, is still limited by: intolerance metal catalysts, inadequate control over chain growth, the absence aromatic system. Monomer design-boosted mechanistic studies may address above challenges. Here, we present a new highly reactive thionolactone synthesized from 1,1'-binaphthyl-2,2'-diol (BINOL). Our investigations into kinetics thermodynamics have underscored importance rapid initiation, eventually leading discovery tetrabutylammonium 2-naphthyl-thiocarboxylate as distinctive initiator that enables genuinely controlled living thionolactones. Ultimately, atropisomerism inherent in BINOL has resulted creation axially chiral PTE materials with tailored molecular weights, enantiomeric compositions, topologies.

Language: Английский

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Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

Abstract Degradable chalcogenide polyesters, e.g., polythioesters (PTEs), typically exhibit improved thermal, mechanical, and optical properties. Anionic ring‐opening polymerization (ROP) of thionolactones, an intrinsically promising yet underexplored approach to accessing PTEs, however, is still limited by: intolerance metal catalysts, inadequate control over chain growth, the absence aromatic system. Monomer design‐boosted mechanistic studies may address above challenges. Here, we present a new highly reactive thionolactone synthesized from 1,1′‐binaphthyl‐2,2′‐diol (BINOL). Our investigations into kinetics thermodynamics have underscored importance rapid initiation, eventually leading discovery tetrabutylammonium 2‐naphthyl‐thiocarboxylate as distinctive initiator that enables genuinely controlled living thionolactones. Ultimately, atropisomerism inherent in BINOL has resulted creation axially chiral PTE materials with tailored molecular weights, enantiomeric compositions, topologies.

Language: Английский

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Enantioselective Catalytic Synthesis of Inherently Chiral Calixarenes

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Since the introduction of concept inherent chirality by Böhmer, an important part research focused on asymmetric synthesis calixarene macrocycles. However, long synthetic procedures and tedious separation strategies hampered application this technology in many topics organic chemistry, including enantioselective molecular recognition catalysis. Very recently, a new generation catalytic methodologies has been reported, able to provide highly functionalized, inherently chiral calixarenes straightforward manner. In review, we will discuss these methods versatile properties such macrocycles that call for potential applications areas science.

Language: Английский

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Functional Bis/Multimacrocyclic Materials Based on Cycloparaphenylene Carbon Nanorings

Accounts of Materials Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Language: Английский

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Chiral covalent organic cages: Construction and chiral functions

Smart Molecules, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Abstract Covalent organic cages (COCs) are three‐dimensional molecules with permanent cavities, known for their ordered pore structures, excellent processability, and modular design. They have shown significant potential in applications such as gas adsorption, molecular separation, catalysis. Introducing chiral elements into COCs results confined which endows them unique functions expands application prospects. This review summarizes the research progress on covalent cages, focusing strategies incorporating elements, structures synthesis methods of representative COCs, advancements functions. Additionally, we provide perspectives future directions. We hope this will inspire further interest creativity among researchers field leading to development materials

Language: Английский

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1,1′-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 26454 - 26465

Published: Sept. 10, 2024

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures accessible high-spin states. However, the synthesis challenging, stability issue remains concern. In this study, we present stable non-Kekulé 1,1'-biolympicenyl diradical

Language: Английский

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Helical-Sense Matching Facilitates Supramolecular Copolymerization of Helical–Chiral Pillar[5]arenes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31816 - 31824

Published: Nov. 11, 2024

Supramolecular polymerization using two-dimensional π-conjugated chiral monomers has been mainly demonstrated because the supramolecular can be controlled by stereocommunication through π-π stacking between monomers. We herein report copolymerization utilizing three-dimensional pentahedrons with twisted helical chirality different combinations of helical-chiral acidic and basic pillar[5]arenes as comonomers. In this case, helical-sense matching is key to facilitating copolymerization. Based on unique pillared structure alternate ion-pairing interactions groups their bilateral rims, homochiral system forms kinetically stable nanowire-shaped copolymers, generating gel in high concentrations. At elevated temperatures, nanowire undergoes a transformation into thermodynamically nanoparticles, resulting gel-to-sol transition. This process hindered introducing linear guest molecules, which prohibit unit swing stabilize nanowires gel. By tailoring enantiomeric ratio (e.r.) values combinations, helical-sense-dependent transition was realized, specifically decreasing e.r. values. Because mismatching, heterochiral generates short, branched presents turbid solution. These distinct differences reveal that pillar[5]arene comonomers important for

Language: Английский

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Chiral synthetic hosts for efficient enantioselective molecular recognition. Design principles and synthetic aspects.

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 24, 2024

Discrimination of enantiomeric substrate molecules is one the fundamental properties biological hosts. Replicating enantioselective molecular recognition with synthetic receptors a topic interest implications in diverse applications such as bioinspired catalysis, enantiomer separation, or sensing. In this review, five different systems reported literature are discussed, and their performance versatility analyzed. A recently host featuring flexible scaffold challenges long-established view that high degree preorganization combination strongly directional non-covalent interactions required for efficient enantiodiscrimination. The review complemented an analysis effort each hosts presented.

Language: Английский

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Preparation of a 1,1'‐Binaphthyl‐based Chiral Polyimine Macrocycle Bonded Chiral Stationary Phase by Thiol‐ene Click Reaction and Its Enantioseparation Performance in High‐Performance Liquid Chromatography

Journal of Separation Science, Journal Year: 2024, Volume and Issue: 47(24)

Published: Dec. 1, 2024

ABSTRACT Chiral macrocycles have emerged as attractive media for chromatographic enantioseparation due to their excellent host‐guest recognition properties. In this study, a new chiral stationary phase (CSP) based on 1,1'‐binaphthyl polyimine macrocycle (CPM) was reported. The CPM synthesized by one‐step aldehyde‐amine condensation of ( S )‐2,2'‐dihydroxy‐[1,1'‐binaphthalene]‐3,3'‐dicarboxaldehyde with 1,2‐phenylenediamine and bonded thiolated silica via the thiol‐ene click reaction afford CSP. performance CSP evaluated separating different types racemates including alcohols, esters, ketones, amides, organic acids, ethers in both normal‐phase (NP) reversed‐phase (RP) elution modes. As result, enantioseparations 10 15 were achieved two modes, respectively. Meanwhile, effects conditions separation, such mobile composition injection mass, studied detail. Moreover, comparison proposed separation tested commercial Chiralcel OD‐H Chiralpak AD‐H columns also conducted, results revealed that can achieve some cannot be columns. This study indicates is promising selector high‐performance liquid chromatography.

Language: Английский

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