A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.
TL;DR: The present review is devoted to summarizing the recent advances (2015–2017) in the field of metal-catalysed group-directed C–H functionalisation.
Abstract: 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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TL;DR: This review broadly discusses various C-H bond functionalization reactions for the formation of C-C bonds with the aid of bidentate directing groups.
Abstract: During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for the expedient and siteselective construction of C–C bonds. Among the v...
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TL;DR: Through discussing the role of NHC ligands in promoting challenging C-H activation methods, the reader is provided with an overview of this important area and its crucial role in forging carbon-carbon and carbon-heteroatom bonds by directly engaging ubiquitous C- H bonds.
Abstract: In this contribution, we provide a comprehensive overview of C-H activation methods promoted by NHC-transition metal complexes, covering the literature since 2002 (the year of the first report on metal-NHC-catalyzed C-H activation) through June 2019, focusing on both NHC ligands and C-H activation methods. This review covers C-H activation reactions catalyzed by group 8 to 11 NHC-metal complexes. Through discussing the role of NHC ligands in promoting challenging C-H activation methods, the reader is provided with an overview of this important area and its crucial role in forging carbon-carbon and carbon-heteroatom bonds by directly engaging ubiquitous C-H bonds.
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"A comprehensive overview of directi..." refers background in this paper
...A ketone directed C-H activation for a enantioselective hydroarylative and hydrovinylative cyclizations were presented by the group Shibata (Table 15, Entry 34).(377) They also stated a possible mechanism for the presented cyclization, which follows a (1) directed C-H activation of an enone, (2) a hydrorhodation of the diyne or enyene and (3) intramolecular carborhodation followed by the generation of the thermodynamically favoured product....
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01 Jun 2005
3,154 citations
"A comprehensive overview of directi..." refers methods in this paper
...In the same year also a Co-catalyzed carbenoid insertion was published using diazo malonates as coupling partners (Table 4, Entry 11).(144) One of the earliest examples using pyrazole as DG was reported by Chatani and coworkers (Table 4, Entry 12)....
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TL;DR: The motivation for studying Pd-catalyzed C-H functionalization assisted by weakly coordinating functional groups is discussed, and efforts to bring reactions of this type to fruition are chronicle.
Abstract: Reactions that convert carbon–hydrogen (C–H) bonds into carbon–carbon (C–C) or carbon–heteroatom (C–Y) bonds are attractive tools for organic chemists, potentially expediting the synthesis of target molecules through new disconnections in retrosynthetic analysis. Despite extensive inorganic and organometallic study of the insertion of homogeneous metal species into unactivated C–H bonds, practical applications of this technology in organic chemistry are still rare. Only in the past decade have metal-catalyzed C–H functionalization reactions become more widely utilized in organic synthesis.Research in the area of homogeneous transition metal–catalyzed C–H functionalization can be broadly grouped into two subfields. They reflect different approaches and goals and thus have different challenges and opportunities. One approach involves reactions of completely unfunctionalized aromatic and aliphatic hydrocarbons, which we refer to as “first functionalization”. Here the substrates are nonpolar and hydrophobic a...
2,291 citations