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Open accessJournal ArticleDOI: 10.1039/D0SC05555G

Recent development in transition metal-catalysed C–H olefination

04 Mar 2021-Chemical Science (Royal Society of Chemistry (RSC))-Vol. 12, Iss: 8, pp 2735-2759
Abstract: Transition metal-catalysed functionalizations of inert C–H bonds to construct C–C bonds represent an ideal route in the synthesis of valuable organic molecules. Fine tuning of directing groups, catalysts and ligands has played a crucial role in selective C–H bond (sp2 or sp3) activation. Recent developments in these areas have assured a high level of regioselectivity in C–H olefination reactions. In this review, we have summarized the recent progress in the oxidative olefination of sp2 and sp3 C–H bonds with special emphasis on distal, atroposelective, non-directed sp2 and directed sp3 C–H olefination. The scope, limitation, and mechanism of various transition metal-catalysed olefination reactions have been described briefly.

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29 results found

Journal ArticleDOI: 10.1021/ACS.ORGLETT.1C01040
12 Apr 2021-Organic Letters
Abstract: A new class of bidentate ligands was prepared by a modular approach involving Rh-catalyzed C-H annulation reactions. The resulting conformationally constrained ligands enabled the Pd-catalyzed C-H alkenylation at electron-rich and sterically less hindered positions of electron-rich arenes while promoting the facile oxidation of Pd(0) intermediates by oxygen. This newly introduced ligand class is complementary to the ligands developed for Pd-catalyzed oxidative reactions and may find broad application in transition-metal-catalyzed reactions.

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Topics: Annulation (58%), Denticity (51%)

7 Citations

Journal ArticleDOI: 10.1021/ACS.ORGLETT.1C00646
05 Apr 2021-Organic Letters
Abstract: An efficient Rh(III)-catalyzed aerobic oxidative C-H alkenylation of arylamides with unactivated alkenes is described The olefination reaction was compatible with various substituted arylamides including primary, secondary, and tertiary as well as functionalized unactivated olefins Meanwhile, ortho mono/bis-alkylated arylamides were synthesized in the reaction of arylamides with norbornene In the alkenylation reaction, molecular oxygen along with organic acid was used to regenerate the active catalyst for the next catalytic cycle A possible reaction mechanism involving C-H activation/insertion/β-hydride elimination followed by aerobic oxidation was proposed and supported by the deuterium labeling studies

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Topics: Catalytic cycle (54%), Catalysis (53%), Norbornene (53%) ... read more

4 Citations

Journal ArticleDOI: 10.1021/ACS.ORGLETT.1C01434
Qiyu Zhang1, Xiong Xie2, Jingjing Peng2, Feiyang Chen1  +6 moreInstitutions (2)
01 Jun 2021-Organic Letters
Abstract: An efficient regioselective palladium(II)-catalyzed C(sp2)-H 4-acetoxylation of tryptophan and tryptophan-containing peptides is described. This transformation achieves the direct construction of C-O bonds at the tryptophan C4-position and features good functional group tolerance. The 4-hydroxyl compound was obtained by removing acetyl after C4-acetoxylation of tryptophan derivatives and tryptophan-containing dipeptides. This method provides a novel strategy for the synthesis of 4-substituted tryptophan derivatives and modification of tryptophan-containing peptides.

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Topics: Tryptophan (55%)

2 Citations

Journal ArticleDOI: 10.1039/D1CC02839A
Ming Zhang1, Shan Gao1, Juan Tang1, Ling Chen1  +3 moreInstitutions (2)
Abstract: This feature article details the progress of transition metal-catalyzed stereoselective sp2 and sp3 C-H activation and silylation in the synthesis of chiral organosilicon compounds, and the asymmetric C-H silylation includes intramolecular cyclizing silylation and intermolecular silylation. The silylating reagents include monohydrosilanes, dihydrosilanes, silacylcobutanes and disilanes. In general, catalytic systems include a transition metal salt as the catalyst and a chiral ligand. No external chiral ligand is required in some cases where the chiral substrates act as the source of chirality. Many kinds of silylated compounds with central, axial, planar, or helical chirality have been constructed via C-H activation by asymmetric rhodium, iridium or palladium catalysis. Some pharmacophores and material building blocks were successfully introduced into the target molecules. Some silylated products proved to be useful in medicinal chemistry, synthetic organic chemistry, and materials science. Besides reaction development, mechanisms for stereoselective C-H activation and silylation are also discussed.

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Topics: Chiral ligand (63%), Silylation (62%), Enantioselective synthesis (58%) ... read more

2 Citations

Journal ArticleDOI: 10.1021/ACS.JOC.1C00769
Abstract: Co(III)-catalyzed alkenylation of 2-pyridones by using terminal alkyne as a reaction partner with high regioselectivity has been demonstrated for the first time. The reaction conditions are mild and compatible with a wide range of substrate combinations. It also shows good functional group tolerance. It proceeds through cyclometalation followed by alkyne insertion and protodemetalation steps. The formation of five- and seven-membered cobaltacycle intermediates was also detected through high-resolution mass spectrometry.

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Topics: Alkyne (59%), Regioselectivity (55%)

1 Citations


157 results found

Open accessJournal ArticleDOI: 10.1021/CR900005N
10 Feb 2010-Chemical Reviews
Abstract: Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

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Topics: Heteroatom (52%), Functional group (51%)

3,010 Citations

Journal ArticleDOI: 10.1021/CR100412J
Lutz Ackermann1Institutions (1)
09 Mar 2011-Chemical Reviews
Abstract: The site-selective formation of carbon-carbon bonds through direct functionalizations of otherwise unreactive carbon-hydrogen bonds constitutes an economically attractive strategy for an overall streamlining of sustainable syntheses. In recent decades, intensive research efforts have led to the development of various reaction conditions for challenging C-H bond functionalizations, among which transition-metal-catalyzed transformations arguably constitute thus far the most valuable tool. For instance, the use of inter alia palladium, ruthenium, rhodium, copper, or iron complexes set the stage for chemo-, site-, diastereo-, and/or enantioselective C-H bond functionalizations. Key to success was generally a detailed mechanistic understanding of the elementary C-H bond metalation step, which depending on the nature of the metal fragment can proceed via several distinct reaction pathways. Traditionally, three different modes of action were primarily considered for CH bond metalations, namely, (i) oxidative addition with electronrich late transition metals, (ii) σ-bond metathesis with early transition metals, and (iii) electrophilic activation with electrondeficient late transition metals (Scheme 1). However, more recent mechanistic studies indicated the existence of a continuum of electrophilic, ambiphilic, and nucleophilic interactions. Within this continuum, detailed experimental and computational analysis provided strong evidence for novel C-H bond metalationmechanisms relying on the assistance of a bifunctional ligand bearing an additional Lewis-basic heteroatom, such as that found in (heteroatom-substituted) secondary phosphine oxides or most prominently carboxylates (Scheme 1, iv). This novel insight into the nature of stoichiometric metalations has served as stimulus for the development of novel transformations based on cocatalytic amounts of carboxylates, which significantly broadened the scope of C-H bond functionalizations in recent years, with most remarkable progress being made in palladiumor ruthenium-catalyzed direct arylations and direct alkylations. These carboxylate-assisted C-H bond transformations were mostly proposed to proceed via a mechanism in which metalation takes place via a concerted base-assisted deprotonation. To mechanistically differentiate these intramolecular metalations new acronyms have recently been introduced into the literature, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms and will be used below where appropriate. This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010. Moreover, experimental and computational studies on stoichiometric metalation reactions being of relevance to the mechanism of these catalytic processes are discussed as well. Mechanistically related C-H bond cleavage reactions with ruthenium or iridium complexes bearing monodentate ligands are, however, only covered with respect to their working mode, and transformations with stoichiometric amounts of simple acetate bases are solely included when their mechanism was suggested to proceed by acetate-assisted metalation.

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Topics: Carboxylate (56%)

2,614 Citations

Journal ArticleDOI: 10.1021/CR000013V
19 Feb 2009-Chemical Reviews
Abstract: A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

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2,228 Citations

Open accessJournal ArticleDOI: 10.1021/AR200185G
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...

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Topics: Retrosynthetic analysis (51%)

2,097 Citations

Journal ArticleDOI: 10.1038/NCHEM.1607
Joanna Wencel-Delord1, Frank Glorius2Institutions (2)
01 May 2013-Nature Chemistry
Abstract: The beginning of the twenty-first century has witnessed significant advances in the field of C-H bond activation, and this transformation is now an established piece in the synthetic chemists' toolbox. This methodology has the potential to be used in many different areas of chemistry, for example it provides a perfect opportunity for the late-stage diversification of various kinds of organic scaffolds, ranging from relatively small molecules like drug candidates, to complex polydisperse organic compounds such as polymers. In this way, C-H activation approaches enable relatively straightforward access to a plethora of analogues or can help to streamline the lead-optimization phase. Furthermore, synthetic pathways for the construction of complex organic materials can now be designed that are more atom- and step-economical than previous methods and, in some cases, can be based on synthetic disconnections that are just not possible without C-H activation. This Perspective highlights the potential of metal-catalysed C-H bond activation reactions, which now extend beyond the field of traditional synthetic organic chemistry.

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1,615 Citations

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