Traceless Directing Groups in Sustainable Metal-Catalyzed C–H Activation DOI Open Access
Αθανάσιος Ζαρκαδούλας, Ioanna Zgouleta, Nikolaos V. Tzouras

et al.

Catalysts, Journal Year: 2021, Volume and Issue: 11(5), P. 554 - 554

Published: April 27, 2021

Sustainable transformations towards the production of valuable chemicals constantly attract interest, both in terms academic and applied research. C–H activation has long been scrutinized this regard, given that it offers a straightforward pathway to prepare compounds great significance. In context, directing groups (DG) have paved way for chemical had not achievable using traditional reactions. Few steps, high yields, selectivity inert substrates are some invaluable assets directed catalysis. Additionally, employment traceless (TDG) greatly improves simplifies strategy, enabling realization multi-step reactions one-pot, cascade procedures. Cheap, abundant, readily available transition metal salts complexes can catalyze plethora employing TDGs, usually under low catalyst loadings—rarely stoichiometric amounts, leading greater atom economy milder conditions with increased yields step-economy. This review article summarizes all work done on TDG-assisted catalysis manganese, iron, cobalt, nickel, or copper catalysts, discusses structure-activity relationships observed, by presenting catalytic pathways range reported thus far.

Language: Английский

C–H Activation: Toward Sustainability and Applications DOI Creative Commons
Toryn Dalton,

Teresa Faber,

Frank Glorius

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(2), P. 245 - 261

Published: Feb. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Language: Английский

Citations

583
Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions DOI
Supriya Rej, Amrita Das, Naoto Chatani

et al.

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213683 - 213683

Published: Dec. 9, 2020

Language: Английский

Citations

227
Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer DOI
Xiaoya Yuan, Congcong Wang, Bing Yu

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109517 - 109517

Published: Jan. 21, 2024

Language: Английский

Citations

38
The emergence of the C–H functionalization strategy in medicinal chemistry and drug discovery DOI
Ranjan Jana, Hasina Mamataj Begam,

Enakshi Dinda

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10842 - 10866

Published: Jan. 1, 2021

Owing to the market competitiveness and urgent societal need, an optimum speed of drug discovery is important criterion for successful implementation. Despite rapid ascent artificial intelligence computational bioanalytical techniques accelerate in big pharma, organic synthesis privileged scaffolds predicted silico vitro vivo studies still considered as rate-limiting step. C-H activation latest technology added into chemist's toolbox construction late-stage modification functional molecules achieve desired chemical physical properties. Particularly, elimination prefunctionalization steps, exceptional group tolerance, complexity-to-diversity oriented synthesis, functionalization medicinal expand space. It has immense potential a library molecules, structural required pharmacological properties such absorption, distribution, metabolism, excretion, toxicology (ADMET) attachment reporters proteome profiling, metabolite etc. preclinical studies. Although heterocycle modification, 18F labelling, methylation, via have been reviewed from synthetic standpoint, general overview these protocols aspects not reviewed. In this feature article, we will discuss recent trends methodologies through activation/annulation cascade; arylation sp2-sp2 sp2-sp3 cross-coupling; borylation/silylation introduce linchpin further manipulation; amination N-heterocycles hydrogen bond acceptors; fluorination/fluoroalkylation tune polarity lipophilicity; methylation: methyl magic discovery; peptide macrocyclization therapeutics biologics; fluorescent labelling radiolabelling bioimaging; bioconjugation biology studies; drug-metabolite biodistribution excretion diversification drug-molecules increase efficacy safety; cutting-edge DNA encoded improved chemistry discovery.

Language: Английский

Citations

94
C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives DOI
Lukass Lukasevics, Aleksandrs Cizikovs, Liene Grigorjeva

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10827 - 10841

Published: Jan. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Language: Английский

Citations

69
Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations DOI
Pengfei Yang, Wei Shu

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 21, 2022

Abstract Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, fine chemicals. Thus, the development of direct efficient methods to these structures a tunable manner is highly desirable yet challenging. Herein, catalyst‐controlled synthesis linear from Ni/Co‐catalyzed regio‐ site‐selective hydroalkylations alkenyl with alkyl halides developed. This catalytic protocol features reliable prediction control coupling position alkylation provide orthogonal access identical starting materials. platform unlocks reactivity selectivity nickel hydride cobalt chemistry catalytically repurpose three types under mild conditions.

Language: Английский

Citations

53
Tandem Reactions involving 1,4‐Palladium Migrations DOI
Mengyao Li, Dong Wei, Chen‐Guo Feng

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(15)

Published: June 6, 2022

Abstract Transition‐metal‐catalyzed tandem reactions have become a mainstay in organic chemistry owing to their high atom‐ and step‐economies. Metal‐migration‐based allow the engagement of simple starting materials for incorporating functional groups into certain positions constructing complex scaffolds, which provide novel means that are complementary traditional cross‐coupling or C−H activation processes. In light broad utility 1,4‐Pd migration reaction, this paper reviews its progress past two decades, summarizing process classifying it based on insertion, elimination, transmetalation, bond activation. Special emphasis is placed driving force Pd different mechanisms. Moreover, review also attempts summarize common strategies improving regio‐ site‐selectivities process.

Language: Английский

Citations

44
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

41
Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides DOI
Kelin Wang,

Xia Song,

Yongdi Xin

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Language: Английский

Citations

27
A Guide to Directing Group Removal: 8‐Aminoquinoline DOI
Liam S. Fitzgerald, Miriam L. O’Duill

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(33), P. 8411 - 8436

Published: Feb. 10, 2021

The use of directing groups allows high levels selectivity to be achieved in transition metal-catalyzed transformations. Efficient removal these auxiliaries after successful functionalization, however, can very challenging. This review provides a critical overview strategies used for Daugulis' 8-aminoquinoline (2005-2020), one the most widely N,N-bidentate groups. limitations are discussed and alternative approaches suggested challenging substrates. Our aim is provide comprehensive end-users' guide chemists academia industry who want harness synthetic power groups-and able remove them from their final products.

Language: Английский

Citations

57