3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 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.

Language: Английский

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A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Language: Английский

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Reduction of Nitro Compounds Using 3d-Non-Noble Metal Catalysts

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2611 - 2680

Published: Dec. 5, 2018

The reduction of nitro compounds to the corresponding amines is one most utilized catalytic processes in fine and bulk chemical industry. latest development catalysts with cheap metals like Fe, Co, Ni, Cu has led their tremendous achievements over last years prompting greater application as "standard" catalysts. In this review, we will comprehensively discuss use homogeneous heterogeneous based on non-noble 3d-metals for using various reductants. different systems be revised considering both performances synthetic aspects highlighting also advantages disadvantages.

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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Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2453 - 2523

Published: Oct. 30, 2018

Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies enable the rational in silico catalyst design. The reactivity nontrivial electronic structure effects, common systems based on 3d transition metals, introduce additional complexity that may represent particular challenge standard computational strategies. In this review, we discuss challenges capabilities modern methods reaction mechanisms promoted by metal molecular catalysts. Particular focus will be placed ways addressing multiconfigurational problem calculations role expert bias utilization available methods. development density functionals designed address metals is also discussed. Special emphasis account solvation effects multicomponent nature systems. This followed an overview recent studies processes catalysts metals. Cases involve noninnocent ligands, systems, metal-ligand metal-metal cooperativity, as well modeling complex such metal-organic frameworks are presented. Conventionally, heavily dependent chemical intuition input researcher. Recent developments advanced automated path analysis hold eliminating human-bias from catalysis studies. A brief these approaches presented final section review. paper closed with general concluding remarks.

Language: Английский

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Organic synthesis with the most abundant transition metal–iron: from rust to multitasking catalysts

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(1), P. 243 - 472

Published: Jan. 1, 2021

The promising aspects of iron in synthetic chemistry are being explored for three-four decades as a green and eco-friendly alternative to late transition metals. This present review unveils these rich iron-chemistry towards different transformations.

Language: Английский

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Access to the meta position of arenes through transition metal catalysed C–H bond functionalisation: a focus on metals other than palladium

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 47(1), P. 149 - 171

Published: Oct. 26, 2017

The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play all manner important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis range methodologies available elaborate arene C-H bonds. Regioselectivity an consideration when selecting method those available, it arguably target meta position fewest number. rapid development metal-catalysed bond functionalisation over last few decades has opened new possibilities meta-selective through diverse reactivity metals and their compatibility with wide directing groups. pace discovery such processes grown rapidly five years particular purpose this review examine these but doing so place focus on other than palladium, specific contributions which have been very recently reviewed elsewhere. It hoped will serve highlight reader breadth current strategies mechanisms tackle challenge, may inspire further progress field.

Language: Английский

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Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(14), P. 5675 - 5680

Published: March 22, 2019

The synthesis of a set cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric electronic parameters are mapped. application potential these complexes for asymmetric C-H functionalizations 3d-metals shown by the dihydroisoquinolones from N-chlorobenzamides broad range alkenes. transformation proceeds excellent enantioselectivities up to 99.5:0.5 er high regioselectivities. observed values outperform best rhodium(III)-based methods this reaction type. Moreover, challenging substrates such as alkyl alkenes also react regio- enantioselectivities.

Language: Английский

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Biaryl synthesis with arenediazonium salts: cross-coupling, CH-arylation and annulation reactions

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(4), P. 1150 - 1193

Published: Jan. 1, 2019

Arenediazonium salts are versatile synthons involved in various transformations for the construction of biaryl moieties.

Language: Английский

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Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3452 - 3506

Published: March 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Language: Английский

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