Enantioselective C–H bond functionalization under Co(iii)-catalysis

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3354 - 3369

Published: Jan. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Language: Английский

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Hydrogen-Bonding Network-Enabled Terminal Selective Heteroarylation of Allenamides in Hexafluoroisopropanol

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

Hexafluoroisopropanol (HFIP)-mediated terminal selective heteroarylation of allenamides has been accomplished through H-bonding network-enabled substrate activation in a robust fashion. This strategy features cascade process involving sequential nucleophilic addition followed by electrophilic heteroaromatic substitution and is well suited for late-stage functionalization complex bioactive molecules. The elucidation the underlying mechanism was achieved comprehensive combination several control experiments, kinetic studies, isotopic labeling isolation HFIP-allenamide intermediate adduct.

Language: Английский

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Electroreductive deuteroarylation of alkenes enabled by an organo-mediator

Chemical Science, Journal Year: 2024, Volume and Issue: 15(29), P. 11418 - 11427

Published: Jan. 1, 2024

An environmentally friendly electroreduction approach is disclosed for site-specific introduction of deuterium via anti-Markovnikov selective deuteroarylation alkenes and aryl iodides with bipyridine as a mediator D 2 O ‘D’ source.

Language: Английский

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Electrochemical Site‐Selective Alkylation of Tropones via Formal C(sp³)−C(sp²) Coupling Reaction

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(9), P. 1965 - 1971

Published: March 5, 2024

Abstract The first site‐selective electrochemical alkylation of tropones is realized by reacting 2‐acetoxytropones and redox‐active‐esters (RAEs). electroreductive protocol enables the preparation mono‐ disubstituted in high yields (up to 71%) under very mild conditions. Dedicated voltammetric measurements served for identification as a class valuable trapping agents nucleophilic radical species shed light on whole mechanistic profile. Wide tolerance towards functional groups (27 examples) application late‐stage functionalization bioactive compound ( i. e . Colchicine analogue), emphasize synthetic impact present methodology.

Language: Английский

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C–C and C–N bond formation in electro-oxidation reactions of aromatic compounds

Current Research in Green and Sustainable Chemistry, Journal Year: 2024, Volume and Issue: 8, P. 100406 - 100406

Published: Jan. 1, 2024

Atom-economical, eco-efficient, metal- and chemical oxidant-free formation of C–C C–N bond from C(sp2)−H C(sp3)−H arenes toward the direct synthesis biaryls anilides or N-benzylamides under mild electro-oxidative conditions is described. The products coupling are obtained in up to 88% yields. Aromatic substrates that oxidized at potentials less positive than +2 V have bulky bromine iodine substituents undergo homo-coupling reactions by anodic oxidation form dimers. difficult oxidize (Eox > V) preferentially upon oxidation. presence a chlorine substituent on aromatic ring leads both during electro-oxidation.

Language: Английский

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A Voltage-Controlled Strategy for Modular Shono-Type Amination

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28663 - 28668

Published: Oct. 14, 2024

Shono-type oxidation to generate functionalized heterocycles is a powerful method for late-stage diversification of relevant pharmacophores; however, development beyond oxygen-based nucleophiles remains underdeveloped. The limited scope can often be ascribed constant current electrolysis resulting in potential drifts that oxidize desired nucleophilic partner. Herein, we report voltage-controlled strategy selectively broad substrates, enabling modular C-N bond formation from protected amine nucleophiles. We implement an electroanalytically guided workflow using cyclic voltammetry (CV) and differential pulse (DPV) identify potentials across range heterocyclic substrates. Controlled (CPE) generates α-functionalized products moderate good yields carbamate-, sulfonamide-, benzamide-derived importance voltage control further exemplified through systematic study comparing our developed CPE (CCE) protocols. Voltage-guided CCE traditionally optimized reveal the maintaining high selectivity over scope; case with morpholine-derived substrate illustrates negative impact drifting under CCE. Sulfonamide drugs, which have significant overlap model are rendered competent CPE. Lastly, sequential C-O functionalization difunctionalized pyrrolidines broadening utility this reaction.

Language: Английский

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Electrocatalysis: Prospects and Role to Enable an E‐Chemistry Future

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract Electrocatalysis is a crucial technology that will enable future low‐carbon chemical production and energy beyond fossil fuels. Notwithstanding the intense growing research in area, potentialities of field are largely unexplored. We provide case examples discuss emerging possibilities have still not been investigated enough but necessary to exploit this potential e‐chemistry. Starting from defining trends setting scene, as well clarifying difference between electrochemistry electrocatalysis, some elements vision foster innovation discussed. The aim stimulate discussion reflection rather than review state‐of‐the‐art. Aspects discussed regard i) passing electro photoelectrocatalytic approaches, ii) making chemicals air, iii) exploitation both anodic cathodic reactions, tandem/paired electrocatalytic iv) for selective oxidation mediated synthesis. Priorities strategies an e‐chemistry Intensifying these directions extending still‐too‐limited current including modelling design, effort accelerate realisation distributed

Language: Английский

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Electrochemical Preparation and Transformation of Sulfonium Salts

ChemElectroChem, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Abstract Sulfonium salts are typically bench‐stable and readily available reagents that showcase diverse chemical reactivities. Owing to these synthetically valuable features, sulfonium salt chemistry has witnessed considerable momentum over the past decades. Particularly, merger of electrosynthesis enabled utilization electric current in place cost‐intensive hazardous redox agents maximize attractive characteristics salts. Additionally, electrochemistry allowed chemists dial desired potential, offering selective access target products otherwise unattainable by either thermal or photochemical manifolds. These advantages led major advances chemistry. Thus, we, herein, provide an overview early pioneering findings recent progress devoted organic associated with until December 2024, aiming stimulate future this rapidly evolving arena.

Language: Английский

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Synthesis of amides via TBN-induced oxidation cross-coupling of acetonitrile and N -sulfinylanilines

Synthetic Communications, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 9

Published: April 21, 2025

Language: Английский

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Electrochemical oxidative CF₃ radical-induced lactonization and etherification of terminal and internal alkenes

RSC Advances, Journal Year: 2025, Volume and Issue: 15(19), P. 15302 - 15309

Published: Jan. 1, 2025

Introducing CF 3 groups boosts drug properties by enhancing metabolic stability and bioavailability. This study reports an electrochemical oxidative difunctionalization of flexible alkenes to form -substituted lactones cyclic ethers.

Language: Английский

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