Anion‐(π)_n‐π Catalytic Micelles

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 14, 2023

Abstract Anion‐π catalysis operates by stabilizing anionic transition states on π‐acidic aromatic surfaces. In anion‐(π) n ‐π catalysis, π stacks add polarizability to strengthen interactions. search of synthetic methods extend beyond the limits foldamers, self‐assembly micelles from amphiphilic naphthalenediimides (NDIs) is introduced. To interface substrates and catalysts, charge‐transfer complexes with dialkoxynaphthalenes (DANs), a classic in supramolecular chemistry, are installed. π‐stacked micelles, rates bioinspired ether cyclizations exceed monomers organic solvents far. This particularly impressive considering that anion‐π water has been elusive so Increasing increasing acidity evince operational catalysis. At maximal acidity, autocatalytic behavior emerges. Dependence position order confined micellar space promises access emergent properties. Anion‐(π) catalytic thus expand systems accessible interactions an inspiring topic general interest great perspectives.

Язык: Английский

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Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Abstract N-Heterocyclic nitreniums (NHNs) are isoelectronic and isostructural analogues of N-heterocyclic carbenes (NHCs). Unlike NHCs, NHNs much less developed. While a comprehensive understanding NHN reactivity remains elusive, recent advancements have demonstrated their utility as Lewis acid catalysts, photoreductants, photooxidants, leading to several reaction patterns. In this short review, we focus on the applications in photoredox reactions. We also discuss mechanisms behind these transformations outline future research directions. 1 Introduction 2 Application Nitreniums Photoreductants 3 Facilitate Photohomolysis 4 Photooxidants 5 Conclusion

Язык: Английский

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Square Planar Pt(II) Ion as Electron Donor in Pnictogen Bonding Interactions

Inorganics, Год журнала: 2023, Номер 11(2), С. 80 - 80

Опубликована: Фев. 15, 2023

It has been proposed that late transition metals with low coordination numbers (square planar or linear) can act as nucleophiles and participate in σ-hole interactions electron donors. This is due to the existence, this type of metal complexes, a pair electrons located at high energy d-orbitals (dz2 dx2-y2), which are adequate for interacting antibonding σ-orbitals [σ*(X–Y)] where Y usually an withdrawing element X p-block. d[M]→σ*(X–Y) interaction reported groups 9–11 oxidation states +1 +2 (d8 d10) donors σ-holes halogen chalcogen atoms acceptors. To our knowledge, it not described pnictogen atoms. In manuscript, evidence existence bonding involving square Pt(II) donor Sb acceptor provided by using X-ray structure retrieved from Cambridge Structural Database (CSD) theoretical calculations. particular, quantum theory molecules (QTAIM), noncovalent plot (NCIPlot) molecular electrostatic potential (MEP) methods were used. Moreover, further confirm nature Sb···Pt(II) contact, recently developed method was used density (ED) (ESP) distribution compared along bond path.

Язык: Английский

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Pnictogen‐Bonding Enzymes

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 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.

Язык: Английский

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Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 24, 2024

Our interest in the design of heavy pnictogen-based Lewis acids for anion trafficking across biological membrane mimics has led us to investigate trivalent bismuthenium cations as chloride transporters. Here, we describe two chlorodiarylbismuthines, elaborated on a peri-substituted naphthalene backbone and stabilized by an adjacent thio- or seleno-ether functionality that engages bismuth center Ch→Bi interaction (Ch=chalcogen). These new derivatives are stable aqueous environment readiliy transport anions phospholipid-based vesicles loaded with KCl. In addition establishing use such motifs transport, this investigation shows acidity, lipophilicity, thus properties depend nature chalcogen.

Язык: Английский

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Steric Selection of Anion Binding Sites by Organoantimony(V) Pnictogen Bond Donors: An Experimental and Computational Study

Inorganic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 3, 2024

Catecholatostiboranes have emerged as useful Lewis acids in several applications. To better understand the factors that control properties of these species, we examined acidities (o-C6Cl4O2)Sb(o-Tol)3 (2, Tol = tolyl) and (o-C6Cl4O2)Sb(p-Tol)3 (3), two triarylcatecholatostiboranes differ by nature aryl substituent. Fluoride anion binding studies indicate 3 is more acidic than 2, a factor readily assigned to steric crowding around antimony case o-tolyl derivative. But, while binds F– trans Sb–Caryl bond typical catecholatostiboranes, 2 prefers Sb–O bond. Computational analyses reveal existence σ holes, an activation strain analysis employed elucidate origin stiboranes' anion-binding geometry preferences.

Язык: Английский

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Bismuthenium Cations for the Transport of Chloride Anions via Pnictogen Bonding

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Авг. 24, 2024

Abstract Our interest in the design of heavy pnictogen‐based Lewis acids for anion trafficking across biological membrane mimics has led us to investigate trivalent bismuthenium cations as chloride transporters. Here, we describe two chlorodiarylbismuthines, elaborated on a peri ‐substituted naphthalene backbone and stabilized by an adjacent thio‐ or seleno‐ether functionality that engages bismuth center Ch→Bi interaction (Ch=chalcogen). These new derivatives are stable aqueous environment readiliy transport anions phospholipid‐based vesicles loaded with KCl. In addition establishing use such motifs transport, this investigation shows acidity, lipophilicity, thus properties depend nature chalcogen.

Язык: Английский

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Anion–π catalysis on carbon allotropes

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 1881 - 1894

Опубликована: Дек. 12, 2023

Anion–π catalysis, introduced in 2013, stands for the stabilization of anionic transition states on π-acidic aromatic surfaces. catalysis carbon allotropes is particularly attractive because high polarizability promises access to really strong anion–π interactions. With these expectations, fullerenes has been 2017, followed by nanotubes 2019. Consistent with expectations from theory, generally increases polarizability. Realized examples reach enolate addition chemistry asymmetric Diels–Alder reactions and autocatalytic ether cyclizations. Currently, gains momentum combination electric-field-assisted transformative impact organic synthesis.

Язык: Английский

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Anion‐(π)_n‐π Catalytic Micelles

Angewandte Chemie, Год журнала: 2023, Номер 135(40)

Опубликована: Авг. 14, 2023

Abstract Anion‐π catalysis operates by stabilizing anionic transition states on π‐acidic aromatic surfaces. In anion‐(π) n ‐π catalysis, π stacks add polarizability to strengthen interactions. search of synthetic methods extend beyond the limits foldamers, self‐assembly micelles from amphiphilic naphthalenediimides (NDIs) is introduced. To interface substrates and catalysts, charge‐transfer complexes with dialkoxynaphthalenes (DANs), a classic in supramolecular chemistry, are installed. π‐stacked micelles, rates bioinspired ether cyclizations exceed monomers organic solvents far. This particularly impressive considering that anion‐π water has been elusive so Increasing increasing acidity evince operational catalysis. At maximal acidity, autocatalytic behavior emerges. Dependence position order confined micellar space promises access emergent properties. Anion‐(π) catalytic thus expand systems accessible interactions an inspiring topic general interest great perspectives.

Язык: Английский

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Cross‐Electrophile C−P^III Coupling of Chlorophosphines with Organic Halides: Photoinduced P^III and Aminoalkyl Radical Generation Enabled by Pnictogen Bonding

Angewandte Chemie, Год журнала: 2023, Номер 135(43)

Опубликована: Сен. 5, 2023

Abstract Pnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, development of a straightforward much simpler protocol cross‐electrophile C−P III coupling remains ongoing challenge with organic halides. In this study, we present simple photoinduced PnB‐enabled couplings using readily available chlorophosphines halides via merging single electron transfer (SET) halogen atom (XAT) processes. photomediated transformation, PnB formed between alkyl amines facilitates photogeneration P radicals α ‐aminoalkyl through SET. Subsequently, resulting activate C−X bonds XAT, leading to formation carbon radicals. This methodology offers operational simplicity compatibility both aliphatic aromatic

Язык: Английский

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