Efficient Suzuki-Miyaura Coupling Research Articles

Efficient Suzuki–Miyaura Coupling of Glutarimide Derivatives

Efficient Suzuki–Miyaura Coupling of Glutarimide Derivatives

Suzuki-Miyaura Type Regioselective C-H Arylation of Aromatic Aldehydes by a Transient Directing Strategy.

Herein, we disclose a common approach for palladium-catalyzed direct coupling of the ortho-C-H bond of aromatic aldehydes with various organoboronic reagents by a transient directing strategy. In contrast to widely used cross-coupling reactions of C-H bonds with aryl halides, which generally need silver salt as a halide removal reagent, the method which used BQ/TFA as weak oxidation system for the PdII/Pd0 redox cycle is cost-effective, ecofriendly, and more aligned with green catalysis. This broadly applicable method opens up a new and efficient Suzuki-Miyaura coupling route for the direct formation of carbon-carbon bonds by C-H bond activation.

Suzuki-Miyaura Coupling Enabled by Aryl to Vinyl 1,4-Palladium Migration.

SummaryThe Suzuki-Miyaura coupling is a fundamentally important transformation in modern organic synthesis. The development of new reaction modes for new chemical accessibility and higher synthetic efficiency is still the consistent pursuance in this field. An efficient Suzuki-Miyaura coupling enabled by a controllable 1,4-palladium migration was realized to afford stereodefined multisubstituted olefins and 1,3-dienes. The reaction exhibits remarkable broad substrate scope, excellent functional-group tolerance, versatile conversion with obtained products, and easy scalability. The practicality of this method is highlighted by the aggregation-induced emission feature of the produced olefins and 1,3-dienes, as well as the capability of affording geometric isomer pairs with a marked difference on photoluminescent quantum yield values.

Early Development Scale-Up of a Structurally-Challenging 5-Lipoxygenase Activating Protein (FLAP) Inhibitor

A practical and efficient synthesis of the FLAP inhibitor 1 was developed addressing multiple scale-up and safety concerns posed by the established synthesis and utilized a resolution strategy (replacing supercritical fluid chromatography (SFC) separation) for expedient access to the key structural component of 1: the challenging chiral quaternary center. Also highlighted are in situ IR monitoring, condensation to form the 1,2,4-oxadiazole ring, and an efficient Suzuki-Miyaura coupling.

Immobilized boronic acid for Suzuki–Miyaura coupling: application to the generation of pharmacologically relevant molecules

An efficient Suzuki–Miyaura coupling of immobilized boronic acid for the generation of a variety of biaryl biologically interesting derivatives is reported.

Facile and efficient Suzuki–Miyaura coupling reaction of aryl halides catalyzed by Pd2(dba)3 in ionic liquid/supercritical carbon dioxide biphasic system

A general and efficient catalytic system for Pd2(dba)3-catalyzed ligand-free Suzuki cross-coupling reactions was developed. The cross-couplings of a wide range of aryl halides with various arylboronic acids were feasible under mild conditions in environmental friendly [hmim]NTf2/supercritical CO2 biphasic system employing K2CO3 as a base, which provided in good to high yields to the corresponding products. The catalytic system could be recycled and reused without significant loss of catalytic activity. Additionally, a possible mechanism of the Suzuki cross-coupling reaction is depicted in this paper.

Palladium nanoparticles embedded in metal–organic framework derived porous carbon: synthesis and application for efficient Suzuki–Miyaura coupling reactions

An efficient Pd catalyst supported on novel nanoporous carbon was developed for the Suzuki-Miyaura coupling reaction. The prepared catalyst can be readily recovered and reused 5 times without significant loss of catalytic activity.

Palladium catalyst coordinated in knitting N-heterocyclic carbene porous polymers for efficient Suzuki–Miyaura coupling reactions

Microporous polymers were synthesised using external cross-linked N-heterocyclic carbene and benzene. These materials can serve as ligands to bind metal ions and demonstrated high catalytic activity for efficient Suzuki–Miyaura coupling reactions.

Efficient Suzuki–Miyaura coupling reaction in water: Stabilized Pdo-Montmorillonite clay composites catalyzed reaction

The Pdo-nanoparticles, generated into the nanopores of modified Montmorillonite clay, were evaluated for catalytic performance for the Suzuki–Miyaura cross coupling reactions. The modification of Montmorillonite clay was carried out by activating with H2SO4 under controlled conditions for generating nanopores on the surface for serving as a ‘Host’ for the Pdo-nanoparticles which were prepared in situ by loading of K2PdCl4 through incipient wetness impregnation technique followed by reduction with hydrazine hydrate. The Powder-XRD, SEM-EDX, TEM, N2 adsorption, XPS, etc. analyses were carried out to characterize the stabilized nanoparticles as well as the support. The TEM study reveals that the evenly distributed Pdo-nanoparticles are below 10nm size and exhibit face centred cubic (fcc) lattice geometry. The supported Pdo-nanoparticles exhibit efficient heterogeneous catalytic performance for the Suzuki–Miyaura coupling reactions between different organoboronic acids and aryl halides for preparing the cross-coupling products in 94% isolated yield (maximum) and 100% selectivity in water under ligand free conditions. The nanocatalysts could be recycled at least three consecutive runs with a little loss of their catalytic activities.

Synthetic Studies on Hemicalide: Development of a Convergent Approach toward the C1–C25 Fragment

Synthetic studies on hemicalide, a recently isolated marine natural product displaying highly potent antiproliferative activity and a unique mode of action, have highlighted a reliable Horner-Wadsworth-Emmons olefination to create the C6-C7 alkene and a remarkable efficient Suzuki-Miyaura coupling to form the C15-C16 bond, resulting in the development of a convergent approach toward the C1-C25 fragment.

Covalently Stabilized Pd Clusters in Microporous Polyphenylene: An Efficient Catalyst for Suzuki Reactions Under Aerobic Conditions

A novel catalyst composed of a microporous polyphenylene network and covalently stabilized Pd clusters (Pd/MPP) for highly efficient Suzuki-Miyaura coupling is synthesized with an in-situ one-pot chemical approach, through the catalytic trimerization of 1,3,5-triethynylbenzene. The unique Pd/MPP cluster exhibits very high catalytic activity for a broad scope of Suzuki-Miyaura reactions with short reaction time, good yield, and high turnover number and turnover frequency values, even in aqueous media under aerobic conditions. The strong covalent interaction between Pd and MPP network prevents the agglomeration or leaching of Pd clusters and enables the catalyst to remain highly active, even after a number of cycles.

One-step synthesis of Lycopodium alkaloid (-)-huperzine W via Suzuki-Miyaura coupling

The first total synthesis of (−)-huperzine W (1) has been achieved. Key element of the synthesis is a highly convergent assemblage for the two rings system of target molecule utilizing an efficient Suzuki-Miyaura coupling reaction between chiral iodide 2 and 2-allylpyrrolidinone 4. Evaluation of the AchE inhibition of synthetic huperzine W was also carried out. Electronic Supplementary MaterialSupplementary material is available for this article at 10.1007/s13659-012-0084-2 and is accessible for authorized users.

An Efficient Suzuki–Miyaura Coupling of Aryl Sulfamates and Boronic Acids Catalyzed by NiCl2(dppp)

AbstractThe Suzuki–Miyaura cross‐coupling of aryl sulfamates and boronic acids was investigated by using [1,3‐bis(diphenylphosphanyl)propane]nickel(II) chloride {NiCl2(dppp)} as the catalyst. The results showed that NiCl2(dppp) is a highly active and general catalyst that allows effective Suzuki–Miyaura cross‐coupling of aryl sulfamates with a slight excess amount of the boronic acid (1.2 equiv.) in the presence of a low catalyst loading (generally 1.0–1.5 mol‐%). The method also displays broad generality not only to various aryl sulfamates, but also to an array of boronic acids. Furthermore, various functional groups are tolerated. These apparent advantages make NiCl2(dppp) a practical and reliable catalyst system for the Suzuki–Miyaura coupling of aryl sulfamates.

Room‐Temperature Synthesis of Tetra‐ortho‐Substituted Biaryls by NHC‐Catalyzed Suzuki–Miyaura Couplings

Into the groove: The introduction of a C2-symmetric N-heterocyclic carbene ligand with appropriately substituted naphthyl side chains enables the efficient Suzuki–Miyaura coupling to form bulky tetra-ortho-substituted biaryls from aryl bromides and chlorides at room temperature. DFT calculations uncover the subtle steric phenomena at play that lead to the superior catalytic performance. Cyoct=cyclooctyl. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

ChemInform Abstract: Highly Efficient Suzuki—Miyaura Coupling of Aryl Tosylates and Mesylates Catalyzed by Stable, Cost‐Effective [1,3‐Bis(diphenylphosphino)propane]nickel(II) Chloride [Ni(dppp)Cl2] with only 1 mol% Loading.

AbstractA highly effective, inexpensive catalyst for the Suzuki—Miyaura cross coupling, namely NiCl2(dppp), is presented.

Highly Efficient Suzuki–Miyaura Coupling of Aryl Tosylates and Mesylates Catalyzed by Stable, Cost‐Effective [1,3‐Bis(diphenylphosphino)propane]nickel(II) Chloride [Ni(dppp)Cl2] with only 1 mol% Loading

AbstractWe present a highly active, inexpensive, universally applicable, and markedly stable [1,3‐bis(diphenylphosphino)propane]nickel(II) chloride [Ni(dppp)Cl2] catalyst that is capable of effecting the Suzuki–Miyaura cross‐coupling of the inherently less reactive but readily available aryl tosylates and mesylates with only 1 mol% loading and in the absence of extra supporting ligand. Under the optimized reaction conditions, cross‐coupling of a wide range of activated, non‐activated, and deactivated, as well as sterically hindered and heteroaromatic substrates (36 examples) could proceed efficiently to afford the coupled products in 53–99% yields. Consequently, the results presented in this work provide a significant advance in Suzuki–Miyaura cross‐coupling in terms of generality, practicality, and cost which are key concerns in recent research regarding transition metal‐catalyzed cross‐couplings.

Synthesis of (E)- and (Z)-Tamoxifen

(Z)-Tamoxifen is used for the treatment of estrogen receptor positive breast cancer. The synthesis depicted features a syn-carbopalladation of alkynyl borate B followed by a 1,2-aryl migration (C → D) to generate a trisubstituted ­alkenylborane in high yield and stereoselectivity. Oxidation of the alkenylbornane D with Me3NO afforded the alkenylborinic ester E that participated in an efficient Suzuki-Miyaura coupling to give (Z)-tamoxifen.

ChemInform Abstract: Efficient Suzuki—Miyaura Coupling of Deactivated Aryl Chlorides Catalyzed by an Oxime Palladacycle.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Efficient Suzuki-Miyaura Coupling of Deactivated Aryl Chlorides Catalyzed by an Oxime Palladacycle

Financial support from the MEC (Projects CTQ2004-00808/BQU, CTQ2007-62771/BQU and Consolider INGENIO 2010 CSD2007-00006), from the Generalitat Valenciana (Projects GV/2007/142 and PROMETEO/2009/039), and the University of Alicante.

ChemInform Abstract: Highly Efficient Suzuki—Miyaura Coupling of Heterocyclic Substrates Through Rational Reaction Design.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.