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

Asymmetric gold catalysis enabled by specially designed ligands DOI
Amol B. Gade,

Urvashi Urvashi,

Nitin T. Patil

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1858 - 1895

Published: Jan. 1, 2024

This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.

Language: Английский

Citations

13
Catalytic Enantioselective Protonation of Gold Enolates Enabled by Cooperative Gold(I) Catalysis DOI

Kaylaa L. Gutman,

Carlos D. Quintanilla, Liming Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3598 - 3602

Published: Jan. 31, 2024

Enantioselective protonation is a versatile approach to the construction of tertiary α-stereocenters, which are common structural motifs in various natural products and biologically relevant compounds. Herein we report mild access these chiral centers using cooperative gold(I) catalysis. From cyclic ketone enol carbonates, this asymmetric catalysis provides highly enantioselective ketones featuring an α center, including challenging 2-methylsuberone. In combination with gold-catalyzed formation cyclopentadienyl carbonates one-pot, two-step process, chemistry enables expedient synthetically α′-chiral cyclopentenones excellent enantiomeric excesses from easily accessible enynyl carbonate substrates.

Language: Английский

Citations

8
Enantioselective merged gold/organocatalysis DOI
Chayanika Pegu, Bidisha Paroi, Nitin T. Patil

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(27), P. 3607 - 3623

Published: Jan. 1, 2024

This highlight demonstrates the state of art in field enantioselective merged gold/organocatalysis by leveraging unique reactivity each catalyst.

Language: Английский

Citations

8
Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates DOI
Rui Wu,

Zurong Xu,

Dong Zhu

et al.

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

Published: Jan. 31, 2025

ConspectusFunctionalization of alkynes is an established cornerstone organic synthesis. While numerous transition metals exhibit promising activities in the transformations via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with through π-bonding, facilitate nucleophilic addition, leading to formation alkenyl metal species. These species can undergo electron rearrangement generate carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides versatile route alkyne functionalization, especially asymmetric manner. Although π-acid, gold(I), pioneered this mode, development variants remains challenging due linear coordination gold(I). Therefore, expanding range catalysts beyond gold(I) complexes other would further advances chiral molecule construction and exploration novel modes.In Account, we present concise review multifunctionalization dirhodium-catalyzed transformations, providing modulation strategies substrates plausible mechanisms. In aromatization-driven strategy, furanyl dirhodium generated from enynone, terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, Büchner reaction, giving dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, cyclohepta[b]benzofurans. The cap-tether strategy was developed study balance reactivity selectivity azo-enyne. gave first catalytic cycloisomerization azo-enyne, affording centrally axially isoindazole derivatives. synergistic activation i.e., EWG C-H···O interaction, introduced achieve enynes, cyclopropane-annulated bicyclic systems enynals. Benefiting these successes, difluoromethyl-substituted enynes were designed proven be effective substrates. With corresponding benzo-1,6-enynes as substrates, biscyclopropanation cascaded cyclopropanation/cyclopropenation achieved using dicarbene equivalents. Additionally, benzo-1,5-enynal vinyl carbene, reacted variety alkenes [2 + 1] cycloaddition, [4 3] formal allylation, spiro fused polycyclic heterocycles. Coupling desymmetrization, successfully diynals, constructing furan-fused dihydropiperidines alkyne-substituted aza-quaternary stereocenter. Notably, analyzing X-ray structures several dirhodium-alkyne π-complexes, together results DFT calculations control experiments, obtained evidence supporting making well-defined paddlewheel-like dirhodium(II) stand out among complexes. We anticipate that our research will significantly advance fields dirhodium, alkyne, chemistry.

Language: Английский

Citations

1
Enantioselective transition-metal catalysis via an anion-binding approach DOI
John M. Ovian, Petra Vojáčková, Eric N. Jacobsen

et al.

Nature, Journal Year: 2023, Volume and Issue: 616(7955), P. 84 - 89

Published: Feb. 14, 2023

Language: Английский

Citations

19
Enantioselective para‐C(sp2)−H Functionalization of Alkyl Benzene Derivatives via Cooperative Catalysis of Gold/Chiral Brønsted Acid** DOI

Xun‐Shen Liu,

Zhiqiong Tang,

Zhi‐Yao Si

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 4, 2022

Abstract An asymmetric para‐ C(sp 2 )−H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis gold and chiral phosphoric acid (CPA), leading to synthetically useful 1,1‐diaryl motifs. Chiral acid, ligand, molecular sieves were found be crucial for enantioselectivity control this transformation. The salient features protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo‐ site‐ as well enantioselective aromatic C−H functionalization, broad substrate scope, extensive applications the products. mechanistic studies suggested that two CPAs might involved in induction.

Language: Английский

Citations

26
Redox Activation of Acyclic (Aryl)(amino)carbene Gold(I) Complexes DOI

Maurice P. Schrick,

G. Kabelo Ramollo, Cristina‐Maria Hirschbiegel

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(2), P. 69 - 84

Published: Jan. 8, 2024

Activation of halido gold(I) precatalysts Au(L)X to a cationic species [Au(L)]+ with vacant coordination site for substrate binding typically requires abstraction the halide X–. The Fischer-type carbene 2–4 feature redox-active dimethylanilinyl, 2-furyl, and ferrocenyl substituents without (2a–4a) (2b–4b), dangling dimethylamino substituent. After single-electron oxidation, catalyze cyclization N(2-propyn-1-yl)benzamide 2-phenyl-5-vinylidene-2-oxazoline presence scavenger. While all dimethylanilinyl 2-furyl substituted likely form catalytically active nanoparticles after complexes 4a 4b operate in homogeneous fashion. precatalyst is most one. formation molecular oxidation was probed by stopped-flow experiments, quantitative EPR spectroscopy, quantum chemical calculations arrive at consistent mechanistic picture that involves one-electron ferrocene, valence isomerization gold(II) anion center. This oxidation/isomerization/coordination activation mechanism fundamentally different from typical opens new avenues gold catalysis beyond gold(III) catalyses.

Language: Английский

Citations

5
Chiral Bifunctional Phosphine Ligand Enables Asymmetric Trapping of Catalytic Vinyl Gold Carbene Species DOI

Xuan Wu,

Ke Zhao, Carlos D. Quintanilla

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2308 - 2312

Published: Jan. 18, 2024

Bifunctional ligand-enabled cooperative gold catalysis accelerates nucleophilic attacks and offers a versatile strategy to achieve asymmetric catalysis. Distinct from the prior studies employing alkyne/allene as electrophilic site, this work engages an in situ-generated alkenyl/acyl carbene ligand-facilitated attack by alcoholic nucleophile. With amide-functionalized chiral binaphthylphosphine ligand, γ-alkoxy-α,β-unsaturated imides are formed with excellent enantiomeric excesses. The intermediacy of species is supported its alternative access via dediazotization. reaction tolerates broad range alcohols can accommodate dienynamide substrates, addition arylenynamides. This avails enrich chemistry challenging enantioselective trapping reactive intermediates.

Language: Английский

Citations

5
Enantioselective Catalysis with Pyrrolidinyl Gold(I) Complexes: DFT and NEST Analysis of the Chiral Binding Pocket DOI Creative Commons
Giuseppe Zuccarello, Leonardo J. Nannini, Ana Arroyo‐Bondía

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 3(6), P. 1742 - 1754

Published: May 26, 2023

A new generation of chiral gold(I) catalysts based on variations complexes with JohnPhos-type ligands a remote C2-symmetric 2,5-diarylpyrrolidine have been synthesized different substitutions at the top and bottom aryl rings: from replacing phosphine by N-heterocyclic carbene (NHC) to increasing steric hindrance bis- or tris-biphenylphosphine scaffolds, directly attaching C2-chiral pyrrolidine in ortho-position dialkylphenyl phosphine. The tested intramolecular [4+2] cycloaddition arylalkynes alkenes atroposelective synthesis 2-arylindoles. Interestingly, simpler led formation opposite enantiomers. binding pockets analyzed DFT calculations. As revealed non-covalent interaction plots, attractive interactions between substrates direct specific enantioselective folding. Furthermore, we introduced open-source tool NEST, specifically designed account for effects cylindrical-shaped complexes, which allows predicting experimental enantioselectivities our systems.

Language: Английский

Citations

12
Silver(I)/Dirhodium(II) Catalytic Platform for Asymmetric N–H Insertion Reaction of Heteroaromatics DOI
Shingo Harada,

Shumpei Hirose,

Mizuki Takamura

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 733 - 741

Published: Dec. 27, 2023

Transition-metal-catalyzed enantioselective N–H insertion reactions of carbene species offer a powerful and straightforward strategy to produce chiral nitrogen-containing compounds. Developing highly selective using indole variants can meet synthetic demand. Herein we present an asymmetric reaction into bonds the aromatic heterocycles donor/acceptor-substituted diazo compounds based on heteronuclear catalytic platform. Although previously developed catalysis comprising silver catalyst or dirhodium(II,II) paddlewheel complexes with without phosphoric acid showed modest performance, unique combination widely available Rh2(OAc)4 silver(I) phosphate dimer [(S)-TRIP-Ag]2 enabled (up 98% ee). Moreover, Ag/Rh system facilitated regioselective C–H functionalization protic indoles. Mechanistic investigation density functional theory indicated that in situ-generated Ag–Rh trimetallic enolate is protonated environment.

Language: Английский

Citations

12