Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

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Electrochemical C–H phosphorylation of arenes in continuous flow suitable for late-stage functionalization

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Nov. 16, 2021

Abstract The development of efficient and sustainable methods for carbon-phosphorus bond formation is great importance due to the wide application organophosphorus compounds in chemistry, material sciences biology. Previous C–H phosphorylation reactions under nonelectrochemical or electrochemical conditions require directing groups, transition metal catalysts, chemical oxidants suffer from limited scope. Herein we disclose a catalyst- external oxidant-free, reaction arenes continuous flow synthesis aryl phosphorus compounds. C–P formed through with anodically generated P-radical cations, class reactive intermediates remained unexplored despite intensive studies P-radicals. high reactivity cations coupled mild electrosynthesis ensures not only diverse electronic properties but also selective late-stage functionalization complex natural products bioactive synthetic utility method further demonstrated by production 55.0 grams one phosphonate products.

Language: Английский

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Electrocatalytic hydrogenation of quinolines with water over a fluorine-modified cobalt catalyst

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 8, 2022

Abstract Room temperature and selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines using a safe clean hydrogen donor catalyzed by cost-effective materials is significant yet challenging because the difficult activation H 2 . Here, fluorine-modified cobalt catalyst synthesized via electroreduction Co(OH)F precursor that exhibits high activity for electrocatalytic O as source produce with up 99% selectivity 94% isolated yield under ambient conditions. Fluorine surface-sites are shown enhance adsorption promote water active atomic (H*) forming F − -K + (H O) 7 networks. A 1,4/2,3-addition pathway involving H* proposed through combining experimental theoretical results. Wide substrate scopes, scalable synthesis bioactive precursors, facile preparation deuterated analogues, paired 1,2,3,4-tetrahydroquinoline industrially important adiponitrile at low voltage highlight promising applications this methodology.

Language: Английский

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Nickel-catalyzed switchable asymmetric electrochemical functionalization of alkenes

Science Advances, Journal Year: 2022, Volume and Issue: 8(45)

Published: Nov. 9, 2022

The development of general electrocatalytic methods for the diversity-oriented regio- and stereoselective functionalization alkenes remains a challenge in organic synthesis. We present switchable method based on anodic oxidative activation controlled liberation chiral α-keto radical species toward transformations. Electrogenerated capture alkene partners, allowing intermolecular difunctionalization alkenylation highly manner. In addition to acting as proton donors facilitate H2 evolution at cathode, unique properties alcohol additives play an important role determining distinct outcomes under conditions.

Language: Английский

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Electrochemical NiH‐Catalyzed C(sp³)−C(sp³) Coupling of Alkyl Halides and Alkyl Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkenes for the construction Csp3 -Csp3 bonds is firstly reported. Notably, serve dual function as substrates hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature this reaction realized by introducing intramolecular coordinating group substrate, where product can be easily adjusted give desired branched products. method proceeds mild conditions, exhibits a broad substrate scope, affords moderate excellent yields with over 70 examples, including late-stage modification natural products drug derivatives. Mechanistic insights offer evidence process. sp3 -carbon-halogen activated through single electron transfer (SET) nickel catalyst in its low valence state, generated cathodic reduction, generation from pivotal transformation.

Language: Английский

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Recent advances in the electrochemical synthesis of organophosphorus compounds

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 770 - 797

Published: April 16, 2025

In this review, we describe recent advances in electrochemical green methods for the synthesis of various organophosphorus compounds through formation phosphorus–carbon, phosphorus–nitrogen, phosphorus–oxygen, phosphorus–sulfur, and phosphorus–selenium bonds. The impact different electrodes is also discussed matter. Graphite, platinum, RVC, nickel have been used extensively compounds. made method a promising preparing structures. This review an introduction to encourage scientists use electrosynthesis as green, precise, low-cost prepare phosphorous

Language: Английский

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Distal Ruthenaelectro‐Catalyzed meta‐C−H Bromination with Aqueous HBr

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(20)

Published: Feb. 16, 2022

While electrochemical ortho-selective C-H activations are well established, distal continue to be underdeveloped. In contrast, we herein describe the meta-C-H functionalization. The remote bromination was accomplished in an undivided cell by RuCl

Language: Английский

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Ruthenaelectro-catalyzed C–H acyloxylation for late-stage tyrosine and oligopeptide diversification

Chemical Science, Journal Year: 2022, Volume and Issue: 13(12), P. 3461 - 3467

Published: Jan. 1, 2022

Ruthenaelectro( ii / iv )-catalyzed intermolecular C–H acyloxylations of oligopeptides have been developed by the guidance key experimental, CV and computational insights.

Language: Английский

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Recent advances in electrochemical C—H phosphorylation

Frontiers in Chemistry, Journal Year: 2022, Volume and Issue: 10

Published: Nov. 3, 2022

The activation of C–H bond, and its direct one-step functionalization, is one the key synthetic methodologies that provides access to a variety practically significant compounds. Particular attention focused on modifications obtained at final stages synthesis complicated molecules, which requires high tolerance presence existing functional groups. Phosphorus an indispensable element life, phosphorus chemistry now experiencing renaissance due new emerging applications in medicinal chemistry, materials (polymers, flame retardants, organic electronics, photonics), agricultural (herbicides, insecticides), catalysis (ligands) other important areas science technology. In this regard, search for new, more selective, low-waste routes become relevant. context, electrosynthesis has proven be eco-efficient convenient approach many respects, where reagents are replaced by electrodes, reactants applied potential determines their “oxidizing or reducing ability”. An electrochemical such processes being developed rapidly demonstrates some advantages over traditional classical methods C-H phosphorylation. main reasons success exclusion excess from reaction system: as oxidants, agents, sometimes metal and/or improvers, challenge isolation, increase wastes reduce yield frequent incompatibility with these Ideal conditions include electron reactant (regulated potential) by-products hydrogen hydrocarbon. review summarizes analyzes achievements preparation various derivatives carbon-phosphorus bonds, collects data redox properties most commonly used precursors. Electrochemically induced reactions both without catalyst metals, competitive oxidation precursors leads either bond generation phosphorus-centered radicals (radical cations) states will examined. focuses publications past 5 years.

Language: Английский

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Recent advances in organic electrochemical functionalizations for specialty chemicals

Current Opinion in Electrochemistry, Journal Year: 2023, Volume and Issue: 40, P. 101312 - 101312

Published: May 20, 2023

Language: Английский

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