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Journal ArticleDOI: 10.1039/D0CY02059A

Suzuki–Miyaura cross coupling reaction: recent advancements in catalysis and organic synthesis

02 Mar 2021-Catalysis Science & Technology (The Royal Society of Chemistry)-Vol. 11, Iss: 4, pp 1186-1221
Abstract: For more than 30 years, palladium has been extensively employed in the Suzuki–Miyaura cross coupling reaction (SMCR) for the synthesis of C–C coupled products. However, Pd-based reactions are associated with higher cost of the synthetic protocols, tedious work-ups, product contamination and metal leaching. In view of this scenario, other metals such as Ni, Cu, Co, Fe, Rh and Ru have gathered the attention of researchers for their usage in SMCR with a wide range of electrophiles that could lead the synthesis of industrially important compounds with various functional groups. In this review, we have discussed the advancements (within the last 4 years) in catalysis related to SMCR that would be beneficial for researchers in designing synthetic protocols for the preparation of pharmacophores as well as drug molecules.

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Topics: Organic synthesis (50%)

14 results found

Open accessJournal Article
01 Jan 2020-Synthesis
Abstract: Cross-coupling reactions have developed into powerful approaches for carbon–carbon bond formation. In this work, a Ni-catalyzed migratory Suzuki–Miyaura cross-coupling featuring high benzylic or allylic selectivity has been developed. With this method, unactivated alkyl electrophiles and aryl or vinyl boronic acids can be efficiently transferred to diarylalkane or allylbenzene derivatives under mild conditions. Importantly, unactivated alkyl chlorides can also be successfully used as the coupling partners. To demonstrate the applicability of this method, we showcase that this strategy can serve as a platform for the synthesis of terminal, partially deuterium-labeled molecules from readily accessible starting materials. Experimental studies suggest that migratory cross-coupling products are generated from Ni(0/II) catalytic cycle. Theoretical calculations indicate that the chain-walking occurs at a neutral nickel complex rather than a cationic one. In addition, the original-site cross-coupling products can be obtained by alternating the ligand, wherein the formation of the products has been rationalized by a radical chain process. Migratory cross-coupling reactions are powerful tools to form bonds at predictable positions. Here the authors report a nickel-catalyzed migratory Suzuki–Miyaura cross-coupling of unactivated alkyl electrophiles with aryl and vinyl boron reagents and provide experimental and computational mechanistic evidence.

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27 Citations

Open access
01 Jan 2013-
Abstract: The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr2·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

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Topics: Electrophile (57%), Umpolung (55%), Alkyl (54%) ... show more

1 Citations

Journal ArticleDOI: 10.1039/D1CC02295D
Abstract: Asymmetric allylic C–H alkylation of 1,4-pentadienes with α-angelica lactones has been developed by tri-axial phosphoramidite-palladium catalysis. This reaction can tolerate a range of functional groups under mild conditions, furnishing versatile chiral γ,γ-disubstituted butenolides in high yields with good to high levels of stereoselectivity.

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Topics: Allylic rearrangement (56%), Alkylation (52%), Stereoselectivity (51%)

1 Citations

Journal ArticleDOI: 10.1039/D1CC04083A
Abstract: Owing to the market competitiveness and urgent societal need, an optimum speed of drug discovery is an important criterion for successful implementation. Despite the rapid ascent of artificial intelligence and computational and bioanalytical techniques to accelerate drug discovery in big pharma, organic synthesis of privileged scaffolds predicted in silico for in vitro and in vivo studies is still considered as the rate-limiting step. C-H activation is the latest technology added into an organic chemist's toolbox for the rapid construction and late-stage modification of functional molecules to achieve the desired chemical and physical properties. Particularly, elimination of prefunctionalization steps, exceptional functional group tolerance, complexity-to-diversity oriented synthesis, and late-stage functionalization of privileged medicinal scaffolds expand the chemical space. It has immense potential for the rapid synthesis of a library of molecules, structural modification to achieve the required pharmacological properties such as absorption, distribution, metabolism, excretion, toxicology (ADMET) and attachment of chemical reporters for proteome profiling, metabolite synthesis, etc. for preclinical studies. Although heterocycle synthesis, late-stage drug modification, 18F labelling, methylation, etc. via C-H functionalization have been reviewed from the synthetic standpoint, a general overview of these protocols from medicinal and drug discovery aspects has not been reviewed. In this feature article, we will discuss the recent trends of C-H activation methodologies such as synthesis of medicinal scaffolds through C-H activation/annulation cascade; C-H arylation for sp2-sp2 and sp2-sp3 cross-coupling; C-H borylation/silylation to introduce a functional linchpin for further manipulation; C-H amination for N-heterocycles and hydrogen bond acceptors; C-H fluorination/fluoroalkylation to tune polarity and lipophilicity; C-H methylation: methyl magic in drug discovery; peptide modification and macrocyclization for therapeutics and biologics; fluorescent labelling and radiolabelling for bioimaging; bioconjugation for chemical biology studies; drug-metabolite synthesis for biodistribution and excretion studies; late-stage diversification of drug-molecules to increase efficacy and safety; cutting-edge DNA encoded library synthesis and improved synthesis of drug molecules via C-H activation in medicinal chemistry and drug discovery.

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Topics: Peptide modification (55%), Drug discovery (55%), Chemical space (53%) ... show more

Journal ArticleDOI: 10.1016/J.JCIS.2021.10.174
Longjiang Sun1, Qi Li1, Mang Zheng1, Siying Lin1  +6 moreInstitutions (2)
Abstract: The development of efficient carbon-carbon cross-coupling catalysts with low noble metal amounts attracts much attention recently. Herein, a Cu/C-700/Pd nanocomposite is obtained by loading trace Pd2+ onto carbon support derived from a novel mononuclear copper complex, {[Cu(POP)2(Phen)2]BF4}. The as-prepared nanomaterial features the facial structure of highly dispersed copper phosphide nanoparticles as well as Pd nanoparticles via neighboring Cu-Pd sites. The Cu/C-700/Pd nanocomposite shows excellent catalytic activity (99.73%) and selectivity in Suzuki-Miyaura cross-coupling reaction, at trace Pd loading (0.43 mol%). Compared with the reported palladium nano catalysts, its advantages are proved. The appealing gateway to this stable, innovative and recyclability, Cu/C-700/Pd nanostructure recommends its beneficial utilization in carbon-carbon coupling and other environmentally friendly processes.

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Topics: Nanocomposite (52%), Palladium (52%), Copper (51%) ... show more


186 results found

Open accessJournal ArticleDOI: 10.1021/CR00039A007
01 Nov 1995-Chemical Reviews
Abstract: B. Other Catalyti; Process by Transition-Metal Complexes IV. Cross-Coupling Reaction A. Coupling of 1 -Alkenylboron Derivatives: Synthesis of Conjugated Dienes 6. Coupling of Arylboron Derivatives: Synthesis of Biaryls C. Coupling of Alkylboron Derivatives D. Coupling with Triflates E. Synthesis of Vinylic Sulfides F. Coupling with lodoalkanes: Alkyl-Alkyl CouDlino G. Coupling with Other Organic Halides and Boron Reagents V. Head-to-Tail Coupling VI. Carbonylative Coupling VII. Alkoxycarbonylation and Dimerization VIII. Conclusion 2457 2458 2458

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Topics: Palladium-catalyzed coupling reactions (60%), Hiyama coupling (58%), Coupling reaction (56%) ... show more

10,584 Citations

Journal ArticleDOI: 10.1002/ANIE.200602866
12 Feb 2007-Angewandte Chemie
Abstract: This review focuses on the synthesis, protection, functionalization, and application of magnetic nanoparticles, as well as the magnetic properties of nanostructured systems. Substantial progress in the size and shape control of magnetic nanoparticles has been made by developing methods such as co-precipitation, thermal decomposition and/or reduction, micelle synthesis, and hydrothermal synthesis. A major challenge still is protection against corrosion, and therefore suitable protection strategies will be emphasized, for example, surfactant/polymer coating, silica coating and carbon coating of magnetic nanoparticles or embedding them in a matrix/support. Properly protected magnetic nanoparticles can be used as building blocks for the fabrication of various functional systems, and their application in catalysis and biotechnology will be briefly reviewed. Finally, some future trends and perspectives in these research areas will be outlined.

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Topics: Magnetic nanoparticles (59%)

5,507 Citations

Open accessJournal ArticleDOI: 10.1002/ANIE.200806273
29 Jun 2009-Angewandte Chemie
Abstract: Pick your Pd partners: A number of catalytic systems have been developed for palladium-catalyzed CH activation/CC bond formation. Recent studies concerning the palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed. In the past decade, palladium-catalyzed CH activation/CC bond-forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming CC bonds from CH bonds: PdII/Pd0, PdII/PdIV, Pd0/PdII/PdIV, and Pd0/PdII catalysis. A more detailed discussion is then directed towards the recent development of palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle. Despite the progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge.

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Topics: Coupling reaction (51%)

3,302 Citations

Open accessJournal ArticleDOI: 10.1016/S0040-4039(01)95429-2
Norio Miyaura1, Kinji Yamada1, Akira Suzuki1Institutions (1)
Abstract: The representative (E)-1-alkenyldisiamylboranes and (E)-1-alkenyl-1,3,2-benzodioxaboroles readily obtainable via hydroboration of 1-alkynes react with 1-alkenyl halides or 1-alkynyl halides in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium and base to give corresponding conjugated (E)-dienes or (E)-enynes with high regio- and stereospecificity in good yields, respectively.

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Topics: Triphenylphosphine (54%), Hydroboration (53%), Palladium (53%) ... show more

1,549 Citations

Journal ArticleDOI: 10.1021/CR300068P
09 Oct 2012-Chemical Reviews
Abstract: Biocompatibility, Pharmaceutical and Biomedical Applications L. Harivardhan Reddy,†,‡ Jose ́ L. Arias, Julien Nicolas,† and Patrick Couvreur*,† †Laboratoire de Physico-Chimie, Pharmacotechnie et Biopharmacie, Universite ́ Paris-Sud XI, UMR CNRS 8612, Faculte ́ de Pharmacie, IFR 141, 5 rue Jean-Baptiste Cleḿent, F-92296 Chat̂enay-Malabry, France Departamento de Farmacia y Tecnología Farmaceútica, Facultad de Farmacia, Campus Universitario de Cartuja s/n, Universidad de Granada, 18071 Granada, Spain ‡Pharmaceutical Sciences Department, Sanofi, 13 Quai Jules Guesdes, F-94403 Vitry-sur-Seine, France

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1,486 Citations