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
TL;DR: 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 are discussed.
About: This article is published in Catalysis Science & Technology.The article was published on 2021-03-02. It has received 68 citations till now. The article focuses on the topics: Organic synthesis.
Citations
More filters
•
TL;DR: A nickel-catalyzed migratory Suzuki–Miyaura cross-coupling featuring high benzylic or allylic selectivity and unactivated alkyl electrophiles and aryl or vinyl boronic acids can be efficiently transferred to diarylalkane or allylbenzene derivatives under mild conditions.
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.
41 citations
••
TL;DR: In this paper , the reader is introduced to an intriguing research subject not yet fully explored and waiting for improved understanding, namely, organic transformations that, although impossible in solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation and expanding the chemical space.
Abstract: Abstract Mechanochemical transformations have made chemists enter unknown territories, forcing a different chemistry perspective. While questioning or revisiting familiar concepts belonging to solution chemistry, mechanochemistry has broken new ground, especially in the panorama of organic synthesis. Not only does it foster new “thinking outside the box”, but it also has opened new reaction paths, allowing to overcome the weaknesses of traditional chemistry exactly where the use of well‐established solution‐based methodologies rules out progress. In this Review, the reader is introduced to an intriguing research subject not yet fully explored and waiting for improved understanding. Indeed, the study is mainly focused on organic transformations that, although impossible in solution, become possible under mechanochemical processing conditions, simultaneously entailing innovation and expanding the chemical space.
32 citations
••
TL;DR: In this paper, the authors discuss the recent trends of C-H activation methodologies such as synthesis of medicinal scaffolds through a cascade of cascade-based activation and activation/annulation cascade, arylation for sp2sp2 and sp2-sp3 cross-coupling, borylation/silylation to introduce a functional linchpin for further manipulation, amination for N-heterocycles and hydrogen bond acceptors, C-h fluorination/fluoroalkylation to tune polarity and lipophilicity, peptide modification and
31 citations
••
TL;DR: In this article , Ru-dithizone@biochar-Ni MNPs were modified by dithizones ligand and then applied for the fabrication of a ruthenium catalyst.
Abstract: Waste recycling and the use of recyclable and available catalysts are important principles in green chemistry in science and industrial research. Therefore in this study, biochar nanoparticles were prepared from biomass pyrolysis. Then, they were magnetized with nickel nanoparticles to improve their recycling. Further, the magnetic biochar nanoparticles (biochar-Ni MNPs) were modified by dithizone ligand and then applied for the fabrication of a ruthenium catalyst (Ru-dithizone@biochar-Ni MNPs). This nanocatalyst was characterized by high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), wavelength dispersive X-ray spectroscopy (WDX), N2 adsorption–desorption isotherms, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM) techniques. The XRD studies of Ru in the nanocatalyst showed that the crystalline structure of ruthenium in the Ru-dithizone@biochar-Ni MNPs was hcp. Another principle of green chemistry is the use of safe and inexpensive solvents, the most suitable of which is water. Therefore, the catalytic activity of this catalyst was investigated as a practical, selective, and recyclable nanocatalyst in the Suzuki carbon–carbon coupling reaction in aqueous media. The VSM curve of this catalyst showed that it could be easily recovered using an external magnet, and recycled multiple times. Also, VSM analysis of the recovered catalyst indicated the good magnetic stability of this catalyst after repeated use.
19 citations
01 Jan 2013
TL;DR: 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.
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.
17 citations
References
More filters
••
TL;DR: In this paper, a cross-coupling reaction is proposed for coupling 1 -Alkenylboron Derivatives: Synthesis of Conjugated Dienes 6.
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
10,937 citations
••
TL;DR: This review focuses on the synthesis, protection, functionalization, and application of magnetic nanoparticles, as well as the magnetic properties of nanostructured systems.
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.
5,956 citations
••
TL;DR: A review of palladium-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle can be found in this paper.
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.
3,533 citations
••
TL;DR: In this article, the representative (E)-1-alkenyldisiamylboranes and 1-alkenyl-1,3,2-benzodioxaboroles readily obtainable via hydroboration of 1 -alkynes react with (1) 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
1,731 citations
••
TL;DR: Biocompatibility, Pharmaceutical and Biomedical Applications L. Harivardhan Reddy,‡ Jose ́ L. Arias, Julien Nicolas,† and Patrick Couvreur*,†.
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
1,705 citations