Endowing Metal‐Organic Coordination Materials with Chiroptical Activity by a Chiral Anion Strategy DOI

Yuanyuan Zhao,

Zhong‐Qiu Li, Zhong‐Liang Gong

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(28)

Published: March 12, 2024

Recently, chiral metal-organic coordination materials have emerged as promising candidates for a wide range of applications in chiroptoelectronics, catalysis, and information encryption, etc. Notably, the chiroptical effect chromophores makes them appealing such photodetectors, OLEDs, 3D displays, bioimaging. The direct synthesis using organic ligands or complexes with metal-centered chirality is very often tedious costly. In case ionic materials, combination anions cationic, achiral compounds through noncovalent interactions may endow molecular desirable properties. use simple strategy has been proven effective inducing circular dichroism and/or circularly polarized luminescence signals. This concept article mainly delves into latest advances exploring efficacy anion transforming superb photo- electro-chiroptical particular, small-molecular metal complexes, clusters, supramolecular assemblies, frameworks containing are discussed. A perspective on future opportunities preparation also presented.

Language: Английский

Fluorinated Biphenyl Phosphine Ligands for Accelerated [Au(I)]-Catalysis DOI
Riccardo Pedrazzani, Sofia Kiriakidi, Magda Monari

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 6128 - 6136

Published: April 8, 2024

Fluorinated JohnPhos-type ligands are proposed as accelerating tools in homogeneous gold(I) catalysis, with PedroPhosAuCl (Cat1) the most efficient one. The well corresponding gold complexes were synthesized high yields and fully characterized also via single-crystal X-ray diffraction. A secondary interaction between distal phenyl ring of phosphane ligand metal center is identified key for fine-tuning overall catalytic performance complexes. In particular, kinetic computational analysis revealed that by accommodating F atoms on biphenyl pendant ligand, more reactive organo-gold intermediates realized toward subsequent nucleophilic condensations. gold-catalyzed indole-hydroarylation 1,6-enynes intramolecular hydroindolynation alkynes have been adopted benchmark reactions to exemplify these effects.

Language: Английский

Citations

4
Practical Synthesis of Chiral Ferrocenenylphosphino-Gold(I) Catalysts and NEST Analysis of the Enantioinduction DOI Creative Commons

P. Mora,

Imma Escofet, María Besora

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2342 - 2350

Published: Jan. 24, 2025

The concise modular synthesis of a family monodentate 1,2-disubstituted ferrocene ligands containing diaryl phosphine and 2-aryl indole is described. Their gold(I) complexes were applied to the enantioselective gold(I)-catalyzed formal [4 + 2] cycloaddition 1,6-arylenynes, enyne cyclization/nucleophile addition N-tethered 1,6-enynes, methoxycyclization 1,6-arylenynes with high levels enantioselectivity in all cases. Crystallographic computational studies highlighted relevant role noncovalent interactions within ligand scaffold between substrate modes enantioinduction cyclization unsaturated substrates. Our recently developed open-source tool NEST was analyze chiral pockets catalysts, which combination RDKit allowed us understand these reactions, paving way for predictive-based approach toward rational development Au(I) catalysis.

Language: Английский

Citations

0
Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis DOI Creative Commons
Harry Adams,

Max Kadarauch,

Nicholas J. Hodson

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Language: Английский

Citations

0
Design and Characterization of Peptide-Based Self-Assembling Microgel for Encapsulation of Sesaminol DOI Creative Commons
Jinhong Gao,

Heng Du,

Zhenhong Zhang

et al.

Foods, Journal Year: 2025, Volume and Issue: 14(6), P. 971 - 971

Published: March 12, 2025

Sesaminol is a natural functional compound of sesame with low bioaccessibility due to its high crystallinity. Here, peptide-based self-assembly microgel was constructed encapsulate sesaminol, reducing crystallinity and improving bioaccessibility. In this contribution, the peptide AcNH-Leu-Tyr-Tyr-CONH2 (LYY) shown form mesoporous three-dimensional (3D) through microstructure characterization. Various characterization methods revealed that LYY self-assembled β-folds random coils, primary intermolecular interactions arose from hydrogen bonding π-π stacking effect. Subsequently, sesaminol encapsulated within co-assembly. The maximum encapsulation efficiency 80.8 ± 0.9%, mainly in nanoparticles by morphology XRD results indicated primarily existed an amorphous state following encapsulation. cumulative release had sustained effect system. Its antioxidant levels were increased. Molecular docking main between structure interactions. Establishing provides valuable data theoretical support for research processing industry.

Language: Английский

Citations

0
Gold-Catalyzed Cascade Reaction of 2-Alkynyl Aryl Azides with Enecarbamates for Direct Synthesis of α-(3-Indolyl)ketones DOI

Jin-Ming Xie,

Yunlong Zhu, Yanming Fu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(2), P. 421 - 425

Published: Jan. 9, 2023

α-(3-Indolyl)ketones are essential building blocks for the generation of biologically active molecules. We described a new method direct assembly α-(3-indolyl)ketones through cascade reaction 2-alkynyl aryl azides with enecarbamates, in which situ generated α-imino gold carbene intermediate was trapped by enecarbamate to achieve umpolung reactivity indole at 3-position.

Language: Английский

Citations

10
Homogeneous Gold Catalysis for Regioselective Carbocyclization of Alkynyl Precursors DOI
Chandrasekar Praveen, Sławomir Szafert

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(7)

Published: June 7, 2023

Abstract π‐Activation of alkynyl precursors possessing an endogenous carbon nucleophile is one the imperative topics in homogeneous gold catalysis as it offers Csp 3 ‐Csp 2 and linked carbocycles. However, exo ‐ dig endo cyclization modes unlocks possibility both small large rings respectively, thereby losing regioselectivity. Nevertheless, several gold‐catalyzed carbocyclizations which permits isomer by controlling or avoiding formation other went largely unnoticed. Hence, this review attempt to summarize such approaches reported from early 2000’s till date along with our viewpoint on contributing parameters for This covers only unimolecular reactions classifications primarily based type nucleophiles silyloxyenols, enamides/enamines, benzenoids, heteroaromatics alkyls/alkenyls. From application perspective, these are significant total synthesis materials science. Therefore, those that finds natural product π‐functional highlighted appropriate places.

Language: Английский

Citations

10
Chiral Auxiliary Approach for Gold(I)‐Catalyzed Cyclizations DOI Creative Commons
Andrea Cataffo,

Miguel Peña‐López,

Riccardo Pedrazzani

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 24, 2023

Two different classes of stereoselective cyclizations have been developed using a chiral auxiliary approach with commercially available [JohnPhosAu(MeCN)SbF6 ] as catalyst. First, cascade cyclization 1,5-enynes was achieved the Oppolzer camphorsultam auxiliary. In this case, one-pot cyclization-hydrolysis sequence to directly afford enantioenriched spirocyclic ketones. Then, alkoxycyclization 1,6-enynes mediated by an Evans-type oxazolidinone. A reduction-hydrolysis selected remove give β-tetralones. DFT studies confirmed that steric clash between and alkene accounts for experimentally observed diastereoselective through Si face.

Language: Английский

Citations

10
Chiral Gold Complex Catalyzed Cycloisomerization/Regio- and Enantioselective Nitroso-Diels–Alder Reaction of 1,6-Diyne Esters with Nitrosobenzenes DOI
Lei Yu, Wenhai Li,

Anyawan Tapdara

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 7288 - 7299

Published: June 3, 2022

An efficient chiral gold(I) complex-catalyzed synthetic method that enables the cycloisomerization/regio- and enantioselective nitroso-Diels–Alder (NDA) reaction of 1,6-diyne esters with nitrosobenzenes is described. The sequential ring formation protocol offers access to a wide variety 3,5,6,8a-tetrahydro-1H-benzo[c][1,2]oxazines as single regioisomer in yields up 99% enantiomeric excess values 99%. This contrast analogous NDA reactions cycloisomerized ester nitrosoarenes absence complex catalytic system, which were found give N,O-heterocyclic product opposite regiochemistry. Experimental computational studies based on postulated dinuclear gold species containing two coordinated nitrosoarene molecules undergoes an asynchronous concerted provides insight into observed regio- enantioselectivities.

Language: Английский

Citations

14
H‐Bonded Counterion‐Directed Catalysis: Enantioselective Gold(I)‐Catalyzed Addition to 2‐Alkynyl Enones as a Case Study DOI Creative Commons
Àlex Martí, Marc Montesinos‐Magraner, Antonio M. Echavarren

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(38)

Published: June 23, 2022

H-bonded counterion-directed catalysis (HCDC) is a strategy wherein chiral anion that hydrogen-bonded to the achiral ligand of metal complex responsible for enantioinduction. In this article we present application Au(I)-catalyzed enantioselective tandem cycloisomerization-addition reaction 2-alkynyl enones. Following addition C-, N- or O-centered nucleophiles, bicyclic furans were obtained in moderate excellent yield and enantioselectivity (28 examples, 59-96 % yield, 62 : 38 95 5 er). The optimal catalytic system, comprising phosphinosquaramide Au(I) chloride BINOL-derived phosphoramidate Ag(I) salt, was selected combinatorial fashion from larger library with help high-throughput screening. An switch ca. 120 Δee% observed upon component salt.

Language: Английский

Citations

14
Enantioselective Au(i)-catalyzed tandem reactions between 2-alkynyl enones and naphthols by the tethered counterion-directed catalysis strategy DOI

Yunliang Yu,

Nazarii Sabat,

Meriem Daghmoum

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 2936 - 2942

Published: Jan. 1, 2023

.The TCDC approach enables tandem cycloisomerization/nucleophilic addition reactions of 2-alkynyl enones with naphthols, good to excellent control the regioselectivity and ees up 99%, under optimized reaction conditions.

Language: Английский

Citations

8