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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Mild metal-catalyzed C–H activation: examples and concepts

Chemical Society Reviews, Год журнала: 2016, Номер 45(10), С. 2900 - 2936

Опубликована: Янв. 1, 2016

C–H Activation reactions that proceed under mild conditions are more attractive for applications in complex molecule synthesis. Mild transformations reported since 2011 reviewed and the different concepts strategies have enabled their mildness discussed.

Язык: Английский

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Cobalt-Catalyzed C–H Activation

ACS Catalysis, Год журнала: 2015, Номер 6(2), С. 498 - 525

Опубликована: Ноя. 24, 2015

Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with development of cobalt-catalyzed functionalizations either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, progress field organometallic is reviewed until November 2015.

Язык: Английский

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Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8908 - 8976

Опубликована: Фев. 17, 2017

The development of new methods for the direct functionalization unactivated C-H bonds is ushering in a paradigm shift field retrosynthetic analysis. In particular, catalytic enantioselective represents highly atom- and step-economic approach toward generation structural complexity. However, as result their ubiquity low reactivity, controlling both chemo- stereoselectivity such processes constitutes significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with emphasis on nature stereochemistry generation. Our analysis serves document considerable rapid progress within field, while also highlighting limitations current methods.

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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Manganese-Catalyzed C–H Activation

ACS Catalysis, Год журнала: 2016, Номер 6(6), С. 3743 - 3752

Опубликована: Апрель 27, 2016

Manganese is found in the active center of numerous enzymes that operate by an outer-sphere homolytic C–H cleavage. Thus, a plethora bioinspired radical-based functionalizations manganese catalysis have been devised during past decades. In contrast, organometallic activation means has emerged only recently as increasingly viable tool organic synthesis. These manganese(I)-catalyzed processes enabled variety with ample scope, which very set stage for substitutive functionalizations. The versatile largely operates isohypsic, thus redox-neutral, mode action through chelation assistance, and provided step-economical access to structurally divers compounds relevance inter alia bioorganic, agrochemical, medicinal chemistry well material sciences.

Язык: Английский

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

ACS Catalysis, Год журнала: 2018, Номер 8(8), С. 7179 - 7189

Опубликована: Июнь 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.

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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Palladium-catalysed norbornene-mediated C–H functionalization of arenes

Nature Chemistry, Год журнала: 2015, Номер 7(11), С. 863 - 870

Опубликована: Окт. 22, 2015

Язык: Английский

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Which Metals are Green for Catalysis? Comparison of the Toxicities of Ni, Cu, Fe, Pd, Pt, Rh, and Au Salts

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(40), С. 12150 - 12162

Опубликована: Авг. 17, 2016

Abstract Environmental profiles for the selected metals were compiled on basis of available data their biological activities. Analysis suggests that concept toxic heavy and safe nontoxic alternatives based lighter should be re‐evaluated. Comparison toxicological indicates palladium, platinum, gold compounds, often considered toxic, may in fact not so dangerous, whereas complexes nickel copper, typically assumed to green sustainable alternatives, possess significant toxicities, which is also greatly affected by solubility water fluids. It appears development new catalysts novel applications rely existing assumptions concerning toxicity/nontoxicity. Overall, experimental seem insufficient accurate evaluation activity these its modulation ligands. Without dedicated measurements particular metal/ligand frameworks, toxicity used as a “selling point” when describing catalysts.

Язык: Английский

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