Metalla-electrocatalyzed C–H Activation by Earth-Abundant 3d Metals and Beyond

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(1), P. 84 - 104

Published: Dec. 19, 2019

To improve the efficacy of molecular syntheses, researchers wish to capitalize upon selective modification otherwise inert C-H bonds. The past two decades have witnessed considerable advances in coordination chemistry that set stage for transformative tools functionalizations. Particularly, oxidative C-H/C-H and C-H/Het-H transformations gained major attention because they avoid all elements substrate prefunctionalization. Despite advances, activations been dominated by precious transition metal catalysts based on palladium, ruthenium, iridium, rhodium, thus compromising sustainable nature overall activation approach. same holds true predominant use stoichiometric chemical oxidants regeneration active catalyst, prominently featuring hypervalent iodine(III), copper(II), silver(I) oxidants. Thereby, quantities undesired byproducts are generated, which preventive applications scale. In contrast, elegant merger homogeneous metal-catalyzed with electrosynthesis bears unique power achieve outstanding levels oxidant resource economy. Thus, contrast classical electrosyntheses control, metalla-electrocatalysis huge largely untapped potential unmet site selectivities means catalyst control. While indirect electrolysis using palladium complexes has realized, less toxic expensive base feature distinct beneficial assets toward this Account, I summarize emergence electrocatalyzed earth-abundant 3d metals beyond, a topical focus contributions from our laboratories through November 2019. cobalt electrocatalysis was identified as particularly powerful platform wealth transformations, including oxygenations nitrogenations well alkynes, alkenes, allenes, isocyanides, carbon monoxide, among others. As complementary tools, nickel, copper, very recently iron devised metalla-electrocatalyzed activations. Key success were detailed mechanistic insights, oxidation-induced reductive elimination scenarios. Likewise, development methods make weak O-coordination benefited crucial insights into catalyst's modes action experiment, operando spectroscopy, computation. Overall, thereby syntheses These electrooxidative frequently characterized improved chemoselectivities. Hence, ability dial redox at minimum level required desired transformation renders an ideal functionalization structurally complex molecules sensitive functional groups. This strategy was, inter alia, successfully applied scale-up continuous flow step-economical assembly polycyclic aromatic hydrocarbons.

Language: Английский

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Recent advances in electrochemical oxidative cross-coupling with hydrogen evolution involving radicals

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10058 - 10086

Published: Jan. 1, 2021

This tutorial review provides an overview of the most recent developments in electrochemical oxidative cross-coupling with hydrogen evolution involving radicals.

Language: Английский

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Electrophotocatalytic Undirected C−H Trifluoromethylations of (Het)Arenes

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(15), P. 3241 - 3246

Published: Dec. 25, 2019

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for generation radical. electrophotochemistry was carried out in an operationally simple manner, setting stage challenging trifluoromethylations unactivated arenes heteroarenes. robust nature electrophotochemical manifold reflected by wide scope, including electron-rich electron-deficient benzenes, as well naturally occurring Electrophotochemical further achieved flow modular electro-flow-cell equipped in-operando monitoring unit on-line flow-NMR spectroscopy, providing support single electron transfer processes.

Language: Английский

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Mn-Catalyzed Electrochemical Radical Cascade Cyclization toward the Synthesis of Benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one Derivatives

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(12), P. 6676 - 6681

Published: May 29, 2020

Benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one derivatives are prevalent in many synthetic intermediates, pharmaceuticals, and organic materials. Herein, we develop a Mn-catalyzed electrochemical radical cascade cyclization reaction that uses electricity as the primary energy input to promote reaction, leading series of benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one under exogenous-oxidant-free conditions. It is worth noting this method can not only realize synthesis but also provides new strategy for generating alkyl radicals from alkylboronic acids.

Language: Английский

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Visible-light-initiated tandem synthesis of difluoromethylated oxindoles in 2-MeTHF under additive-, metal catalyst-, external photosensitizer-free and mild conditions

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(6), P. 1907 - 1910

Published: Jan. 18, 2021

Language: Английский

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Recent advances on electrochemical generation of sulfonyl radical triggered cyclization of alkene/alkynes

Tetrahedron, Journal Year: 2025, Volume and Issue: 173, P. 134467 - 134467

Published: Jan. 12, 2025

Language: Английский

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Electrochemical Minisci-type trifluoromethylation of electron-deficient heterocycles mediated by bromide ions

Organic Chemistry Frontiers, Journal Year: 2019, Volume and Issue: 6(14), P. 2392 - 2397

Published: Jan. 1, 2019

An electrochemical methodology for the Minisci-type trifluoromethylation of electron-deficient heterocycles mediated by cheap and easily available bromide ions has been developed.

Language: Английский

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CF₃SO₂Na as a Bifunctional Reagent: Electrochemical Trifluoromethylation of Alkenes Accompanied by SO₂ Insertion to Access Trifluoromethylated Cyclic N‐Sulfonylimines

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(18), P. 7266 - 7270

Published: Feb. 20, 2020

An unprecedented electrochemical trifluoromethylation/SO2 insertion/cyclization process has been achieved in an undivided cell atom-economic fashion. The protocol relies on tandem cyclization of N-cyanamide alkenes by using Langlois' reagent as a source both CF3 and SO2 under direct anodically oxidative conditions, which two C-C bonds, C-X bonds (N-S S-C), rings were formed single operation. This transformation enabled efficient construction various trifluoromethylated cyclic N-sulfonylimines from readily accessible materials.

Language: Английский

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Progress in Electrochemical Trifluoromethylation Reactions

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(23), P. 5219 - 5237

Published: Oct. 13, 2020

Abstract The importance of fluorinated organic molecules in drugs and pharmaceuticals led to the development several synthetic methods for introducing fluorine into bioactive trifluoromethylation is one key approaches same. Electrochemical synthesis has emerged as most sustainable, green strategies recent years new developments electroorganic also focus on electrochemical compounds. A considerable number reports have appeared literature this review surveys all reactions. This highly sustainable trifluoromethylating protocol will emerge further soon pave way more energy‐efficient protocols. magnified image

Language: Английский

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Electrooxidative dearomatization of biaryls: synthesis of tri- and difluoromethylated spiro[5.5]trienones

Chemical Science, Journal Year: 2021, Volume and Issue: 12(29), P. 10092 - 10096

Published: Jan. 1, 2021

Radical spirocyclization via dearomatization has emerged as an attractive strategy for the rapid synthesis of structurally diverse spiro molecules. We report use electrochemistry to perform oxidative biaryls leading tri- and difluoromethylated spiro[5.5]trienones in a user friendly undivided cell set-up constant current mode. The catalyst- chemical oxidant-free procedure features ample scope, employs electricity green sole oxidant.

Language: Английский

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