Electrocatalytic C–H Activation

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(8), P. 7086 - 7103

Published: June 18, 2018

C–H activation has emerged as a transformative tool in molecular synthesis, but until recently oxidative activations have largely involved the use of stoichiometric amounts expensive and toxic metal oxidants, compromising overall sustainable nature chemistry. In sharp contrast, electrochemical been identified more efficient strategy that exploits storable electricity place byproduct-generating chemical reagents. Thus, transition-metal catalysts were shown to enable versatile reactions manner. While palladium catalysis set stage for C(sp2)–H C(sp3)–H functionalizations by N-containing directing groups, rhodium ruthenium allowed weakly coordinating amides acids. contrast these precious 4d transition metals, recent year witnessed emergence cobalt oxygenations, nitrogenations, C–C-forming [4+2] alkyne annulations. Thereby, silver(I) oxidants was prevented, improving environmentally benign catalysis. Herein, we summarize major advances organometallic otherwise inert bonds electrocatalysis through May 2018.

Language: Английский

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Transition‐Metal‐Catalyzed Carboxylation Reactions with Carbon Dioxide

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(49), P. 15948 - 15982

Published: May 3, 2018

Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, recent years have witnessed renewed interest in devising catalytic fixations into organic matter. Although formation C-C bonds via fixation remained rather limited for a long period time, close look literature data indicates that carboxylation reactions entered new era exponential growth, evolving mature discipline allows streamlining synthesis carboxylic acids, building blocks utmost relevance industrial endeavors. These strategies generally proven broadly applicability convenient to perform. However, substantial challenges still need be addressed reinforcing cover metal-catalyzed area conceptual concise manner, delineating underlying principles are slowly emerging this vibrant expertise.

Language: Английский

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A Survival Guide for the “Electro-curious”

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(1), P. 72 - 83

Published: Dec. 11, 2019

ConspectusThe appeal and promise of synthetic organic electrochemistry have been appreciated over the past century. In terms redox chemistry, which is frequently encountered when forging new bonds, it difficult to conceive a more economical way add or remove electrons than electrochemistry. Indeed, many largest industrial chemical processes are achieved in practical using as reagent. Why then, after so years documented benefits electrochemistry, not widely embraced by mainstream practitioners? Erroneous perceptions that "black box" combined with lack intuitive inexpensive standardized equipment likely contributed this stagnation interest within community. This barrier entry magnified fact can already be accomplished simple reagents even if they less atom-economic. Time has proven sustainability economics strong enough driving forces for adoption electrochemical techniques broader like chemists dabbled age-old technique, our first foray into area was choice but rather through sheer necessity.The unique reactivity old redox-modulating technique must therefore highlighted leveraged order draw field. Enabling bonds forged higher levels chemo- regioselectivity will accomplish goal. doing so, envisioned widespread go beyond supplanting unsustainable mundane reactions development exciting paradigms enable heretofore unimagined retrosynthetic pathways. Whereas rigorous physical principles electroorganic synthesis reviewed elsewhere, often case such summaries leave out pragmatic aspects designing, optimizing, scaling up preparative reactions. Taken together, task setting an reaction, much inventing one, vexing seasoned chemists. Account features format focuses on addressing exact issue context own studies. The graphically rich presentation style pinpoints basic concepts, typical challenges, key insights those "electro-curious" who seek rapidly explore power their research.

Language: Английский

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Expanding the medicinal chemistry synthetic toolbox

Nature Reviews Drug Discovery, Journal Year: 2018, Volume and Issue: 17(10), P. 709 - 727

Published: Aug. 24, 2018

Language: Английский

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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 415 - 431

Published: March 9, 2021

Efficient and selective molecular syntheses are paramount to

Language: Английский

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First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2090 - 2127

Published: May 3, 2018

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. contents divided according to electrophiles applied, followed by different types nucleophiles. Their reaction mechanisms applications emphatically

Language: Английский

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Electro-organic synthesis – a 21^stcentury technique

Chemical Science, Journal Year: 2020, Volume and Issue: 11(46), P. 12386 - 12400

Published: Jan. 1, 2020

This perspective provides insight into recent electro-organic methods and general trends in this field, opens up prospects for future viewpoints.

Language: Английский

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Recent Advances in C–H Functionalization Using Electrochemical Transition Metal Catalysis

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(8), P. 7179 - 7189

Published: June 19, 2018

Electrochemical transition metal catalysis is a powerful strategy for organic synthesis because it obviates the use of stoichiometric chemical oxidants and reductants. C–H bond functionalization offers variety useful conversions simple ubiquitous molecules into diverse functional groups in single synthetic operation. This review summarizes recent progress merging electrochemistry with metal-catalyzed functionalization, specifically C–C, C–X (halogen), C–O, C–P, C–N formation.

Language: Английский

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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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An Electrocatalytic Approach to the Radical Difunctionalization of Alkenes

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(6), P. 5175 - 5187

Published: April 26, 2018

Given its many distinct characteristics, electrochemistry represents an attractive approach to meet the prevailing trends in organic synthesis. In particular, electrocatalysis—a process that integrates and small-molecule catalysis—has potential substantially improve scope of synthetic provide a wide range useful transformations. Recently, we have demonstrated new catalytic approaches combine redox-metal catalysis for oxidative difunctionalization alkenes access diverse array vicinally functionalized structures. This Perspective details our design principles underpinning development electrochemical diazidation, dichlorination, halotrifluoromethylation alkenes, which were built on foundational work by others areas electrochemistry, radical chemistry, transition-metal catalysis. The introduction redox-active Mn catalysts allows generation intermediates from readily available reagents at low potentials under mild conditions. These transition metals also impart selectivity control over alkene functionalization processes functioning as group transfer agents. As such, electrocatalytic reactions exhibit excellent chemoselectivity, broad substrate scope, high functional compatibility. Specifically, anodically coupled electrolysis, pairs two single-electron oxidation events parallel manner, enables regio- chemoselective heterodifunctionalization alkenes. products transformations describe this represent pertinent structures numerous medicinally relevant compounds. We anticipate parameters presented here are general will platform systems other challenging redox

Language: Английский

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