3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

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Recent Advances in Oxidative R¹-H/R²-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry

Chemical Reviews, Год журнала: 2019, Номер 119(12), С. 6769 - 6787

Опубликована: Май 10, 2019

Photo-/electrochemical catalyzed oxidative R1-H/R2-H cross-coupling with hydrogen evolution has become an increasingly important issue for molecular synthesis. The dream of construction C-C/C-X bonds from readily available C-H/X-H release H2 can be facilely achieved without external chemical oxidants, providing a greener model bond formation. Given the great influence these reactions in organic chemistry, we give summary state art via photo/electrochemistry, and hope this review will stimulate development synthetic strategy near future.

Язык: Английский

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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Год журнала: 2021, Номер 7(3), С. 415 - 431

Опубликована: Март 9, 2021

Efficient and selective molecular syntheses are paramount to

Язык: Английский

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

Accounts of Chemical Research, Год журнала: 2019, Номер 53(1), С. 84 - 104

Опубликована: Дек. 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.

Язык: Английский

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Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3180 - 3218

Опубликована: Ноя. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Язык: Английский

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Resource Economy by Metallaelectrocatalysis: Merging Electrochemistry and C H Activation

Trends in Chemistry, Год журнала: 2019, Номер 1(1), С. 63 - 76

Опубликована: Март 8, 2019

Язык: Английский

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3d metallaelectrocatalysis for resource economical syntheses

Chemical Society Reviews, Год журнала: 2020, Номер 49(13), С. 4254 - 4272

Опубликована: Янв. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Язык: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 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.

Язык: Английский

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Iridium‐Catalyzed Electrooxidative C−H Activation by Chemoselective Redox‐Catalyst Cooperation

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(43), С. 14179 - 14183

Опубликована: Сен. 10, 2018

Iridium-catalyzed electrochemical C-H activation was accomplished within a cooperative catalysis manifold, setting the stage for electrooxidative alkenylations through weak O-coordination. The iridium-electrocatalyzed featured high functional-group tolerance assistance of metal-free redox mediator indirect electrolysis. Detailed mechanistic insights provided strong support an organometallic cleavage and synergistic iridium(III/I)/redox catalyst regime, enabling use sustainable electricity as terminal oxidant with improved selectivity features.

Язык: Английский

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