Control of Selectivity in Homogeneous Catalysis through Noncovalent Interactions

Chemistry - A European Journal, Год журнала: 2023, Номер 29(26)

Опубликована: Фев. 23, 2023

The regio-, site-, stereo- or chemoselective homogeneous catalytic transformations are extremely important for the growth/success of current chemical industry. Based on empirical, theoretical intuitive knowledge, several synthetic strategies, such as ligand design, transient directing group, metal node alternation, metal-ligand cooperation, pore decoration, biomimetic, have already been developed selective functionalization organic substrates. In comparison to other tactics, use noncovalent interactions control selectivity in compounds may avoid multi-steps, reduce time procedure, decrease cost operation, and increase reactivity catalyst. fact, enzymes achieve a high through biochemical processes Nature. Guided by impressive performance biosynthesis biodegradation reactions, various types complex organocatalysts developed, which catalyst-substrate pivotal impact distinctive stabilization transition states intermediates, improving efficiency reactions. Herein, we highlight recent relevant examples directing/driving function transformation substrate(s) catalyzed both catalysts.

Язык: Английский

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The Matere Bond

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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A Bidentate Antimony Pnictogen Bonding Host System

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Сен. 29, 2023

Abstract A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as Lewis acidic host component for the complexation of basic or anionic guests. In this work, novel C≡C−Sb(C 2 F 5 ) unit established study potential antimony(III) sites representatives scarcely explored donors. The capability partly fluorinated system towards halide anions (Cl − , Br I ), dimethyl chalcogenides Me Y (Y=O, S, Se, Te), nitrogen heterocycles (pyridine, pyrimidine). Insights into adduct formation behavior well situation such E⋅⋅⋅Sb−C moieties were obtained in solution means NMR spectroscopy, solid state X‐ray diffraction, elemental analyses, computational methods (DFT, QTAIM, IQA), respectively.

Язык: Английский

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The Origin of Anion−π Autocatalysis

JACS Au, Год журнала: 2023, Номер 3(4), С. 1039 - 1051

Опубликована: Март 17, 2023

The autocatalysis of epoxide-opening ether cyclizations on the aromatic surface anion−π catalysts stands out as a leading example emergent properties expected from integration unorthodox interactions into catalysis. A working hypothesis was proposed early on, but mechanism has never been elucidated. Here, we show that is almost independent peripheral crowding in substrate and product. Inaccessible asymmetric sometimes erratic reproducibility further support origin more complex than originally assumed. apparent long-distance communication without physical contact calls for inclusion water between product catalytic surface. Efficient around equimolar amounts poor activity dry solvents with excess indicate this requires high precision. Computational models suggest two molecules transmit dual activation by serve proton shuttles along antiparallel decoupled hydrogen-bonded chains to delocalize stabilize evolving charge density transition state "anion−π double bonds". This new transition-state model provides plausible explains experimental results brings catalysis an unprecedented level sophistication.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 5, 2023

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-PIII 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 PIII 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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Electric field–assisted anion-π catalysis on carbon nanotubes in electrochemical microfluidic devices

Science Advances, Год журнала: 2023, Номер 9(41)

Опубликована: Окт. 12, 2023

The vision to control the charges migrating during reactions with external electric fields is attractive because of promise general catalysis, emergent properties, and programmable devices. Here, we explore this idea anion-π that stabilization anionic transition states on aromatic surfaces. Catalyst activation by polarization system most effective. This induced fields. use electrochemical microfluidic reactors polarize multiwalled carbon nanotubes as catalysts emerges essential. These provide access high at low enough voltage prevent electron transfer, afford meaningful effective catalyst/substrate ratios, avoid interference from additional electrolytes. Under these conditions, rate pyrene-interfaced epoxide-opening ether cyclizations linearly voltage-dependent positive voltages negligible negative voltages. While electromicrofluidics have been conceived for redox chemistry, our results indicate their supramolecular organocatalysis has potential noncovalently electrify organic synthesis in broadest sense.

Язык: Английский

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A Fluorogenic Substrate for Quinoline Reduction: Pnictogen‐Bonding Catalysis in Aqueous Systems

Helvetica Chimica Acta, Год журнала: 2024, Номер 107(5)

Опубликована: Март 6, 2024

Abstract It is often said that pnictogen‐bonding catalysis, and σ ‐hole catalysis in general, would not work aqueous systems because the solvent interfere as an overcompetitive pnictogen‐bond acceptor. In this study, we show transfer of from hydrophobic solvents to possible by replacing only with hydrophilic substrates, without changing catalyst or reaction. This differs conventional covalent Lewis acid catalysts, which are instantaneously destroyed ligand exchange. With their water‐proof substituents place exchangeable ligands, supramolecular counterpart evinced catalyze hydrogenation quinolines neutral systems. To secure these results, introduce a water‐soluble fluorogenic substrate releases coumarin upon reduction instead activated quinolidiniums, stiborane catalysts deepened holes. They demonstrate can operate higher‐order architectures for under biologically relevant conditions, provide operational assay high‐throughput screening fluorescence imaging, situ conditions.

Язык: Английский

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Pnictogen‐Bonding Enzymes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(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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Poly-pnictogen bonding: trapping halide ions by a tetradentate antimony(iii) Lewis acid

Chemical Science, Год журнала: 2023, Номер 14(46), С. 13551 - 13559

Опубликована: Янв. 1, 2023

A tetradentate host system with four CC–Sb(C 2 F 5 ) functions binds halide ions in a distorted square planar coordination. Experimental and calculated structures reveal complex interplay of attractive pnictogen bonding Coulomb repulsion.

Язык: Английский

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On the Existence of Pnictogen Bonding Interactions in As(III) S‐Adenosylmethionine Methyltransferase Enzymes

Chemistry - An Asian Journal, Год журнала: 2024, Номер 19(8)

Опубликована: Фев. 26, 2024

As(III) S-adenosylmethionine methyltransferases, pivotal enzymes in arsenic metabolism, facilitate the methylation of up to three times. This process predominantly yields trivalent mono- and dimethylarsenite, with trimethylarsine forming smaller amounts. While this enzyme acts as a detoxifier microbial systems by altering As(III), humans, it paradoxically generates more toxic potentially carcinogenic methylated species. The strong affinity for cysteine residues, As(III)-thiolate bonds, is exploited medical treatments, notably trioxide (Trisenox®), an FDA-approved drug leukemia. effectiveness partly due its interaction leading breakdown key oncogenic fusion proteins. In study, we extend understanding As(III)'s binding mechanisms, showing that, addition As(III)-S covalent noncovalent O⋅⋅⋅As pnictogen bonding plays vital role. significantly contributes structural stability complexes. Our crystallographic analysis using PDB database augmented comprehensive theoretical studies including molecular electrostatic potential (MEP), quantum theory atoms molecules (QTAIM), natural bond orbital (NBO) analysis, emphasizes critical role these systems. We also undertake detailed evaluation energy characteristics bonds various models. To our knowledge, first time derivatives have been reported biological systems, marking significant advancement arsenic's interactions.

Язык: Английский

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