Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Sept. 1, 2023

A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access valuable from simple acid feedstocks. This robust method relies on alternating polarity maintain the quality electrode surface local pH, providing a deeper understanding Hofer-Moest process with unprecedented chemoselectivity.

Language: Английский

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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Aug. 22, 2023

Abstract Organic electrosynthesis has consistently aroused significant interest within both academic and industrial spheres. Despite the considerable progress achieved in this field, majority of electrochemical transformations have been conducted through utilization direct‐current (DC) electricity. In contrast, application alternating current (AC), characterized by its polarity‐alternating nature, remains infancy sphere organic synthesis, primarily due to absence a comprehensive theoretical framework. This minireview offers an overview recent advancements AC‐driven seeks elucidate differences between DC AC electrolytic methodologies probing into their underlying physical principles. These encompass ability preclude deposition metal catalysts, precision modulating oxidation reduction intensities, mitigation mass transfer processes.

Language: Английский

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Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Language: Английский

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Recent Advances in the Electrochemical Defluorinative Transformations of C—F Bonds

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(16), P. 1913 - 1928

Published: April 24, 2024

Comprehensive Summary Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation transformation have long been a formidable challenge due to the high energy low reactivity of C—F bonds. electrosynthesis, an environmentally benign synthetic method in chemistry, enables myriad chemical transformations without need for external redox reagents. In recent years, electrochemistry has emerged as powerful tool achieving bonds fluorine‐containing compounds. This review aims succinctly recapitulate latest advancements electrochemical defluorinative delve into reaction design, mechanistic insights, developmental prospects these methods. Key Scientists 1959, Lund was first pioneer electroreduction CF 3 CH group. Electrochemistry lately provided new opportunities efficient conversion fluorides. 2020, Zhou coworkers discovered carboxylation α‐CF alkenes. Lambert colleagues reported electrophotocatalytic amination aryl Electrochemical hydrodefluorination trifluoromethylketones developed by Lennox 2021. same year, Wang Guo disclosed radical alkylation alkenes with Katritzky salts alkyl precursors. Subsequently, Wu Liao described transition‐metal‐free, site‐selective arylation polyfluoroarenes (het)arenes using paired electrophotocatalysis. 2023, numerous efforts were made achieve bond activation. Xia organoboron‐controlled chemoselective sequential (deutero)hydrodefluorination trifluoroacetamides.

Language: Английский

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Electrochemistry for the Chemoselective Modification of Peptides and Proteins

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 23 - 41

Published: Dec. 30, 2021

Although electrochemical strategies for small-molecule synthesis are flourishing, this technology has yet to be fully exploited the mild and chemoselective modification of peptides proteins. With growing number diverse peptide natural products being identified emergence modified proteins as therapeutic diagnostic agents, methods stand alluring prospects harnessing reactivity polypeptides build molecular complexity. As a inherently tunable reaction platform, electrochemistry is arguably well-suited overcome chemo- regioselectivity issues which limit existing bioconjugation strategies. This Perspective will showcase recently developed approaches protein modification. The article also highlights wealth untapped opportunities production homogeneously biomolecules, with an eye toward realizing enormous potential chemistry.

Language: Английский

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Current electrochemical approaches to selective deuteration

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(18), P. 2944 - 2953

Published: Jan. 1, 2022

The selective deuteration of organic molecules through electrochemistry is proving to be an effective alternative conventional 2H labelling strategies, which traditionally require high temperatures, pressures deuterium gas in hydrothermal autoclave reactors, or reagents capable generating highly reactive species are then quenched by a source. Such harsh conditions can consequently lower chemo- regioselectivity many processes. Transition metal catalysis and more recently photocatalysis have emerged as methods access selectively deuterated compounds under significantly mild conditions. Now, electrochemistry, increasingly becoming mainstream synthetic tool, primed enter this space. Accordingly, highlight will feature selection electrochemical developed recent years, propose where the use electrosynthesis could novel reactivity context deuteration.

Language: Английский

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Scalable, Chemoselective Nickel Electrocatalytic Sulfinylation of Aryl Halides with SO₂

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(37)

Published: July 12, 2022

Abstract Simple access to aryl sulfinates from iodides and bromides is reported using an inexpensive Ni‐electrocatalytic protocol. The reaction exhibits a broad scope, uses stock solution of simple SO 2 as sulfur source, can be scaled up in batch recycle flow settings. limitations this are clearly shown put into context by benchmarking with state‐of‐the‐art Pd‐based methods.

Language: Английский

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Controlling One- or Two-Electron Oxidation for Selective Amine Functionalization by Alternating Current Frequency

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(22), P. 9874 - 9882

Published: May 27, 2022

Here, we report a unique electrosynthetic method that enables the selective one-electron oxidation of tertiary amines to generate α-amino radical intermediates over two-electron iminium cations, providing easy access arylation products by simply applying an optimal alternating current (AC) frequency. More importantly, have discovered electrochemical descriptor from cyclic voltammetry studies predict AC frequency for various amine substrates, circumventing time-consuming trial-and-error methods optimizing reaction conditions. This new development in electrolysis provides alternative strategy solving challenging chemoselectivity problems synthetic organic chemistry.

Language: Английский

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Steering the Dynamics of Reaction Intermediates and Catalyst Surface during Electrochemical Pulsed CO₂ Reduction for Enhanced C₂₊ Selectivity

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20655 - 20664

Published: Aug. 28, 2023

Developing alternative electrolysis techniques is crucial for advancing electrocatalysis in addition to tremendous efforts of material developments. Recently, pulse electrochemical CO2 reduction reaction (CO2RR) has demonstrated dramatic selectivity improvement toward multicarbon (C2+) products compared potentiostatic CO2RR, yet the underlying mechanisms remain little understood. Herein, we develop a fast time-resolved situ Raman spectroscopic method with time resolution 0.25 s. We reveal that improves C2+ CO2RR through dynamic controls surface CuxO/Cu composition would be unachievable under electrolysis. The population surface-adsorbed CO intermediate (COads) characterized determining factor controlling selectivity, which depicts C2+/C1 conditions. Meanwhile, vibrational character COads, despite transforming dynamically between low-frequency and high-frequency modes not key selectivity. Such an active control catalyst compositions intermediates enabled by offer general way regulating performance broad reactions beyond CO2RR.

Language: Английский

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Ratcheting synthesis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 8(1), P. 8 - 29

Published: Dec. 15, 2023

Language: Английский

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