The present review is devoted to summarizing the recent advances (2015-2017) in the field of metal-catalysed group-directed C-H functionalisation. In order to clearly showcase the molecular diversity that can now be accessed by means of directed C-H functionalisation, the whole is organized following the directing groups installed on a substrate. Its aim is to be a comprehensive reference work, where a specific directing group can be easily found, together with the transformations which have been carried out with it. Hence, the primary format of this review is schemes accompanied with a concise explanatory text, in which the directing groups are ordered in sections according to their chemical structure. The schemes feature typical substrates used, the products obtained as well as the required reaction conditions. Importantly, each example is commented on with respect to the most important positive features and drawbacks, on aspects such as selectivity, substrate scope, reaction conditions, directing group removal, and greenness. The targeted readership are both experts in the field of C-H functionalisation chemistry (to provide a comprehensive overview of the progress made in the last years) and, even more so, all organic chemists who want to introduce the C-H functionalisation way of thinking for a design of straightforward, efficient and step-economic synthetic routes towards molecules of interest to them. Accordingly, this review should be of particular interest also for scientists from industrial R&D sector. Hence, the overall goal of this review is to promote the application of C-H functionalisation reactions outside the research groups dedicated to method development and establishing it as a valuable reaction archetype in contemporary R&D, comparable to the role cross-coupling reactions play to date.
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http://dx.doi.org/10.1039/c8cs00201k | DOI Listing |
J Xenobiot
December 2024
Department of Chemical Engineering, University of Pretoria, Pretoria 0028, South Africa.
The direct discharge of cationic surfactants into environmental matrices has exponentially increased due to their wide application in many products. These compounds and their degraded products disrupt microbial dynamics, hinder plant survival, and affect human health. Therefore, there is an urgent need to develop electroanalytical assessment techniques for their identification, determination, and monitoring.
View Article and Find Full Text PDFDalton Trans
December 2024
Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 00 Prague, Czech Republic.
C-H bond functionalisation has developed into a powerful synthetic methodology that is applicable to a wide array of substrates, including organometallic compounds. In this study, racemic, planar-chiral 1,2-dihydroferroceno[]isoquinoline and analogous helical compounds with one or two additional -fused benzene rings were synthesised by palladium-catalysed C-H bond activation/cyclisation of -[(bromoaryl)methyl]--(methylsulfonyl)aminoferrocenes. These starting materials are readily accessible from FcNHSOMe (Fc = ferrocenyl) and appropriate vicinal bromo-(bromomethyl)arenes.
View Article and Find Full Text PDFMethods Enzymol
November 2024
Manchester Institute of Biotechnology, University of Manchester, Manchester, United Kingdom. Electronic address:
The microbial UbiX-UbiD system facilitates the reversible (de)carboxylation of alpha, beta-unsaturated carboxylic acids, including aromatic compounds. The direct C-H carboxylation presents an attractive method for functionalisation and carbon capture but is difficult to achieve under mild conditions. Hence, UbiD-mediated Csp2-H activation can serve as a versatile tool for developing new biocatalytic routes to transform aryl or alkene compounds and carbon dioxide into valuable commodity chemicals.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK.
Azoles have widespread applications in medicinal chemistry; for example, thiazoles, imidazoles, benzimidazoles, isoxazoles, tetrazoles and triazoles appear in the top 25 most frequently used N-heterocycles in FDA-approved drugs. Efficient routes for the late-stage C-H functionalisation of azole cores would therefore be highly desirable. The Minisci reaction, a nucleophilic radical addition reaction onto N-heterocyclic bases, is a direct C-H functionalisation reaction that has the potential to be a powerful method for C-H functionalisations of azole scaffolds.
View Article and Find Full Text PDFRSC Adv
September 2024
Bioinspired & Biomimetic Inorganic Chemistry Lab, Department of Chemistry, National Institute of Technology Calicut Kozhikode Kerala 673601 India
Selective functionalisation of hydrocarbons using transition metal complexes has evoked significant research interest in industrial chemistry. However, selective oxidation of unactivated aliphatic C-H bonds is challenging because of the high bond dissociation energies. Herein, we report the synthesis, characterisation and catalytic activity of nickel(ii) complexes ([Ni(L1-L3)(OH)](ClO) (1-3)) of monoamidate tetradentate ligands [L1: 2-(bis(pyridin-2-ylmethyl)amino)--phenylacetamide, L2: 2-(bis(2-pyridin-2-ylmethyl)amino)--(naphthalen-1-yl)acetamide, L3: -benzyl-2-(bis(pyridin-2-ylmethyl)amino)acetamide] in selective oxidation of cycloalkanes using -CPBA as the oxidant.
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