Electricity-driven asymmetric bromocyclization enabled by chiral phosphate anion phase-transfer catalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 23, 2023

Electricity-driven asymmetric catalysis is an emerging powerful tool in organic synthesis. However, induction so far has mainly relied on forming strong bonds with a chiral catalyst. Asymmetry induced by weak interactions catalyst electrochemical medium remains challenging due to compatibility issues related solvent polarity, electrolyte interference, etc. Enabled properly designed phase-transfer strategy, here we have achieved two efficient electricity-driven catalytic bromocyclization processes ion-pairing interaction. The combined use of and phosphate catalyst, together NaBr as the bromine source, constitutes key advantages over conventional chemical oxidation approach. Synergy multiple events, including anodic oxidation, ion exchange, phase transfer, bromination, inhibition Br2 decomposition NaHCO3, proved critical success.

Язык: Английский

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Chiral Induction at the Nanoscale and Spin Selectivity in Electron Transmission in Chiral Methylated BEDT-TTF derivatives

Nanoscale, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) enantiomers’ spin filtering and chiroptical properties are studied. Spin-filtering assessed by recording spin-polarized I – V curves (mc-AFM) of TM-BEDT-TTF fibrils.

Язык: Английский

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Zinc Electrode Cycling in Deep Eutectic Solvent Electrolytes: An Electrochemical Study

Molecules, Год журнала: 2023, Номер 28(3), С. 957 - 957

Опубликована: Янв. 18, 2023

Among post-lithium ion battery technologies, rechargeable chemistries with Zn anodes bear notable technological promise owing to their high theoretical energy density, lower manufacturing cost, availability of raw materials and inherent safety. However, anodes, when employed in aqueous electrolytes, suffer from hydrogen evolution, passivation, shape changes. Alternative electrolytes can help tackle these issues, preserving the green safe characteristics aqueous-based ones. Deep eutectic solvents (DESs) are promising low-cost non-aqueous for electrolytes. Specifically, cycling DESs is expected be reversible, chiefly dendrite-suppression capability. Nevertheless, apart a few studies on plating, insight into cathodic-anodic electrochemistry still very limited. In view developing DES-based it crucial consider that potential drawback might low ionic conductivity. Water molecules added mixtures by up 40% increase diffusion coefficient electroactive species electrolyte viscosity without destroying nature. this study, we address two different hydrated (ChU ChEG ~30% H2O). Fundamental electrokinetic electrocrystallization based cyclic voltammetry chronoamperometry at cathodic substrates completed galvanostatic test Zn|Zn symmetric CR2032 coin cells, SEM imaging electrodes situ SERS spectroscopy. This investigation concludes proposal specific DES/H2O/ZnSO4-based exhibits optimal functional performance, rationalized basis fundamental electrochemical data, morphology evaluation modeling response.

Язык: Английский

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An electrochemical sensor employing β-cyclodextrin chiral cross-linked metal organic framework and graphene oxide for chiral enantiomer recognition

Microchemical Journal, Год журнала: 2022, Номер 183, С. 108074 - 108074

Опубликована: Окт. 25, 2022

Язык: Английский

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Different Impact of Menthol Chirality on Ideal and Deep Eutectic Solvents: Thermal and Structural Insights

Journal of Molecular Liquids, Год журнала: 2025, Номер unknown, С. 127676 - 127676

Опубликована: Апрель 1, 2025

Язык: Английский

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Smart interfaces in Li-ion batteries: Near-future key challenges

Electrochimica Acta, Год журнала: 2022, Номер 415, С. 140258 - 140258

Опубликована: Март 21, 2022

Язык: Английский

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Chiral Solvent Discovery: Exploring Chiral Eutectic Mixtures and Deep Eutectic Solvents

Industrial & Engineering Chemistry Research, Год журнала: 2023, Номер 62(3), С. 1606 - 1613

Опубликована: Янв. 17, 2023

Deep eutectic solvents (DES) are mixtures that have a melting point much lower than any of the components. Because properties DES, such as chiral discrimination, can be controlled through choice components, DES potential in many chemical and industrial applications. However, large number components makes high throughput methods discovery critical for their development. In this study, small quantities hydrogen bond acceptors (HBAs) donors (HBDs) were mixed at 55 °C cooled to 20 screen liquid formation. Variable molar ratios 10 HBAs with 93 HBDs measure total 1250 mixtures, 356 °C. All results including did not form liquids provided publicly available database. Several prepared larger characterize physical properties, points, densities, viscosities. The study used guide development new solvents, mixtures.

Язык: Английский

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Spin-dependent electrochemistry and electrochemical enantioselective recognition with chiral methylated bis(ethylenedithio)-tetrathiafulvalenes

The Journal of Chemical Physics, Год журнала: 2023, Номер 159(20)

Опубликована: Ноя. 28, 2023

Enantio-discrimination and spin-dependent electrochemistry (SDE), as a manifestation of the chirality-induced spin selectivity (CISS) effect, are important phenomena that can be probed by "chiral" electrochemistry. Here, we prepared chiralized surfaces gold nickel, to serve working electrodes, through effective chemisorption enantiopure dimethyl-bis(ethylenedithio)-tetrathiafulvalene (DM-BEDT-TTF) 1, tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) 2, their capped silver nanoparticle (AgNPs) aggregate simple incubation metallic substrates. The was checked means ultrahigh vacuum x-ray photoelectron spectroscopy (XPS) electro-desorption experiments, i.e., cyclic voltammetry (CV) scans showing first peak at about -1.0 V. Au|1 Au|2 chiral electrodes were successfully used in CV experiments exploiting redox probes. Finally, hybrid interfaces Ni|enantiopure 1 or 2|AgNPs served SDE experiments. In particular, Ni|(R)-2|AgNPs Ni|(S)-2|AgNPs exhibited significant spin-filtering ability, CISS with average polarization values 15%.

Язык: Английский

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Enantio‐Recognition and Charge Transfer Complex Formation Involving Tetrathiafulvalene‐Appended Chiral 1,2‐Cyclohexane‐Diamine: An Integrated Experimental and Theoretical Study

Chirality, Год журнала: 2024, Номер 36(12)

Опубликована: Дек. 1, 2024

ABSTRACT In this work, we exploit the electronic features of tetrathiafulvalene (TTF) as a backbone in synthesizing chiral derivatives. The aim is to make use TTF's well‐known and unique redox semiconducting properties fields enantio‐selective recognition charge transfer (CT) complex preparation, with ultimate objective obtaining devices various potential applications, ranging from plasmonics quantum computing. particular, both cyclohexane‐bis (TTF‐amide)–based enantiomers 1‐( S,S ) R,R , stable under an oxidation regime, have been selected, these conditions, electrochemical enantiospecific response four possible systems, coming combination L‐ D‐tartaric acid, respectively, was tested. 1 :tartaric acid adducts show lower potentials than pristine together clear enantio‐discrimination demonstrated by sizeable differences range 29–46 mV between diastereomeric adducts. Because suggests possibility formation CT complexes, impedance FT‐IR spectra were recorded confirm hypothesis case :I 2 . experimental results obtained through analysis also compared theoretical deriving DFT‐based calculations.

Язык: Английский

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Catalytic Enantioselective Synthesis Enabled by Electrochemistry

Synthesis, Год журнала: 2023, Номер 55(18), С. 2926 - 2942

Опубликована: Янв. 12, 2023

Abstract Catalytic enantioselective electrochemical synthesis has emerged in recent years as an efficient, clean, sustainable way to obtain chiral, non-racemic molecules. The difficulties finding reaction conditions that are compatible with the delicate functional groups of many chiral ligands and organocatalysts hampered developments this field. However, fact very minute differences potential can be selected, allows for fine-tuning, so high chemoselectivities achieved, which is attracting much attention. Although still few number compared other areas knowledge, existing methods allow a variety bond-forming reactions performed, yields ees achieved. present review surveys literature published last four years. 1 Introduction 2 Transition-Metal-Catalyzed Reactions 2.1 Alkylation by C–H Bond Functionalization: C(sp3)–C(sp3) Formation 2.2 C(sp3)–C(sp2) 2.2.1 Alkene Functionalization Cross-Coupling 2.2.2 Arylation 2.3 Alkynylation: C(sp3)–C(sp) 2.4 Synthesis Axially Chiral Biaryls 2.5 Cyanofunctionalization 2.6 Miscellaneous 3 Organocatalysis 4 Conclusions

Язык: Английский

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