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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Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Chemical Reviews, Journal Year: 2016, Volume and Issue: 117(13), P. 9163 - 9227

Published: Dec. 12, 2016

The transition-metal-catalyzed addition of C–H bonds to carbonyls, imines, and related polarized π has emerged as a particularly efficient powerful approach for the construction an incredibly diverse array heteroatom-substituted products. Readily available stable inputs are typically employed, reactions often proceed with very high functional group compatibility without production waste byproducts. Additionally, many bond additions occur within cascade reaction sequences provide rapid access different heterocyclic well carbocyclic This review highlights diversity transformations that have been achieved, catalysts used, types products prepared through bonds.

Language: Английский

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(Pentamethylcyclopentadienyl)cobalt(III)‐Catalyzed C–H Bond Functionalization: From Discovery to Unique Reactivity and Selectivity

Advanced Synthesis & Catalysis, Journal Year: 2017, Volume and Issue: 359(8), P. 1245 - 1262

Published: March 16, 2017

Abstract High‐valent (pentamethylcyclopentadienyl)cobalt(III) [Cp*Co(III)] catalysts were found as inexpensive alternatives to (pentamethylcyclopentadienyl)rhodium(III) [Cp*Rh(III)] in the field of C—H bond functionalization, and applied a variety transformations. In this review, after discovery early examples Cp*Co(III)‐catalyzed functionalization are summarized, unique reactivity selectivity Cp*Co(III) differences between cobalt rhodium catalysis intensively discussed. Such assumed be caused by lower electronegativity, hard nature, smaller ionic radius cobalt. magnified image

Language: Английский

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Recent advances in multi-component reactions and their mechanistic insights: a triennium review

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(15), P. 4237 - 4287

Published: Jan. 1, 2021

This review summarizes the recent developments in MCRs, incorporating different strategies along with their mechanistic aspects.

Language: Английский

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C–H functionalization by high-valent Cp*Co(iii) catalysis

Chemical Communications, Journal Year: 2017, Volume and Issue: 53(22), P. 3165 - 3180

Published: Jan. 1, 2017

Significant progress has been accomplished in directed C–H functionalization through the use of earth-abundant and inexpensive first-row transition metals.

Language: Английский

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Enantioselective Cobalt(III)‐Catalyzed C−H Activation Enabled by Chiral Carboxylic Acid Cooperation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15425 - 15429

Published: Oct. 6, 2018

The enantioselective cobalt(III)-catalyzed C-H alkylation was achieved through the design of a novel chiral acid. activation characterized by high position-, regio- and enantio-control under exceedingly mild reaction conditions. Thereby, robust cooperative cobalt(III) catalysis proved tolerant valuable electrophilic functional groups, including hydroxyl, bromo, iodo substituents. Mechanistic studies revealed considerable additive effect on kinetics negative non-linear-effect.

Language: Английский

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Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)‐Catalyzed Intermolecular Carboamination of Alkenes

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(48), P. 15166 - 15170

Published: Oct. 27, 2016

Abstract Herein, we report an unprecedented regioselective and entirely atom‐economic cobalt(III)‐catalyzed method for the non‐annulative, intermolecular carboamination of alkenes. The methodology enables direct synthesis unnatural amino acid derivatives proceeds under redox‐neutral conditions with a completely C−C bond C−N formation. Furthermore, this reaction exemplifies inherently different mechanistic behavior Cp*Co III catalyst its Cp*Rh counterpart, especially towards β‐H‐elimination.

Language: Английский

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Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

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Recent advances in chelation-assisted site- and stereoselective alkenyl C–H functionalization

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(5), P. 3263 - 3314

Published: Jan. 1, 2021

Olefinic C-H functionalization represents an atom- and step economic approach to valuable olefin derivatives from simpler ones, but controlling the selectivity remains a challenge. Remarkable progress has been made in site-selective of arenes alkanes, there are still limited examples selective olefins presumably due lability easy decomposition alkenyl moiety. Chelation-assisted activation efficient protocol for site- stereo-selective construction carbon-carbon carbon-heteroatom bonds. This review highlights recent advances vicinal- geminal-group-directed olefinic functionalization, including alkenylation, arylation, alkynylation, alkylation, halogenation, silylation, cyanation annulation by formation exo-/endo-metallocycles. In particular, is covered first time, as well distal-selective under palladium/norbornene cooperative catalysis, which provides novel disconnections retrosynthetic analysis future trend green chemistry.

Language: Английский

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