Asymmetric Suzuki-Miyaura Coupling Research Articles

Search for Ideal P-Chiral Phosphorus Ligands for Practical Asymmetric Hydrogenation and Asymmetric Suzuki–Miyaura Coupling

The synthesis of P-chiral phosphorus ligands with novel structures is important for the development of efficient asymmetric catalytic transformations. Here, we describe the development of P-chiral phosphorus ligands such as BIBOP, WingPhos, BI-DIME, and <b>8 </b>in our laboratory. Conformational rigidity, high tunability of electronic and steric properties, and convenient physical properties are the main features of our ligand design. Progress in developing practical asymmetric hydrogenation and asymmetric cross-coupling reactions are discussed.

Monodentate Chiral N-Heterocyclic Carbene-Palladium-Catalyzed Asymmetric Suzuki-Miyaura and Kumada Coupling

N-Heterocyclic carbene ligands derived from <i>C</i> ₂-symmetric diamine with naphthyl side chains are introduced as chiral monodentate ligands, and their palladium complexes (NHC)Pd(cin)Cl are prepared. These compounds exist as a mixture of diastereomers, and the palladium complexes can be successfully separated. When used in the asymmetric Suzuki–Miyaura and ­Kumada coupling, chiral biaryls can be obtained in high yield and moderate selectivity.

ChemInform Abstract: Highly Diastereoselective Synthesis of Atropisomeric Bridged P,N‐Ligands and Their Applications in Asymmetric Suzuki—Miyaura Coupling Reaction.

AbstractElectron‐withdrawing groups in the boronic acids lead to diminished the yields and enantioselectivities.

Highly Diastereoselective Synthesis of Atropisomeric Bridged P,N‐Ligands and Their Applications in Asymmetric Suzuki–Miyaura Coupling Reaction

AbstractThree novel atropisomeric bridged P,N‐ligands were prepared using a highly efficient central‐to‐axial transfer strategy as the protocol. The new chiral ligands were successfully applied in the palladium‐catalyzed asymmetric Suzuki–Miyaura coupling reaction, Up to 98% yield and 82% ee were obtained in the enantioselective synthesis of axially chiral biarylphosphonates.

ChemInform Abstract: Highly Efficient Synthesis of a Class of Novel Chiral‐Bridged Atropisomeric Monophosphine Ligands via Simple Desymmetrization and Their Applications in Asymmetric Suzuki—Miyaura Coupling Reaction.

AbstractAmong various derivatives, ligand (I) is found to be the most efficient one to produce axially chiral organophosphorus compounds.

Palladium-Catalyzed Asymmetric Suzuki-Miyaura Coupling

Palladium-Catalyzed Asymmetric Suzuki-Miyaura Coupling

Efficient Chiral Monophosphorus Ligands for Asymmetric Suzuki–Miyaura Coupling Reactions

A series of novel P-chiral monophosphorus ligands exhibit efficiency in asymmetric Suzuki-Miyaura coupling reactions, enabling the construction of an array of chiral biaryl products in high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. The carbonyl-benzooxazolidinone moiety in these chiral biaryl products allows facile derivatization for further synthetic applications. A computational study has revealed that a π-π interaction between the two coupling partners can enhance the enantioselectivity of the coupling reaction.

Highly Efficient Synthesis of a Class of Novel Chiral-Bridged Atropisomeric Monophosphine Ligands via Simple Desymmetrization and Their Applications in Asymmetric Suzuki–Miyaura Coupling Reaction

A series of novel chiral-bridged atropisomeric monophosphine ligands were synthesized via convenient and simple pathways. The prepared ligands, especially for ligand 7d, were found to be highly effective in the Pd-catalyzed Suzuki-Miyaura coupling reaction. The steric hindrance and electronic effect of substrates on the reactivity and enantioselectivity were explored preliminarily.

ChemInform Abstract: Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki—Miyaura Coupling Using High‐Molecular‐Weight, Helically Chiral Polyquinoxaline‐Based Phosphines.

AbstractA new catalyst system is used to synthesize axially chiral biarylphosphonic esters by asymmetric Suzuki—Miyaura coupling of 1‐bromo‐2‐naphthalenephosphonic esters (I) with o‐methyl‐substituted phenylboronic acids.

Synthesis, structure, and catalytic activity of palladium complexes with new chiral cyclohexane-1,2-based di-NHC-ligands

A pair of novel palladium complexes {[(1S,2S)-L]PdBr2} and {[(1R,2R)-L]PdBr2} of chiral di-N-heterocyclic carbene ligands derived from chiral 1,2-cyclohexanediamine have been prepared in moderate to good yields and characterized by NMR, HRMS and X-ray single crystal diffraction studies. The obtained chiral NHC–Pd compound was able to catalyze the asymmetric Suzuki–Miyaura couplings of aryl bromides with arylboronic acids in good yields and moderate enantioselectivities (up to 61% ee).

Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki–Miyaura Coupling Using High‐Molecular‐Weight, Helically Chiral Polyquinoxaline‐Based Phosphines

Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki–Miyaura Coupling Using High‐Molecular‐Weight, Helically Chiral Polyquinoxaline‐Based Phosphines

Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki–Miyaura Coupling Using High‐Molecular‐Weight, Helically Chiral Polyquinoxaline‐Based Phosphines

Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki–Miyaura Coupling Using High‐Molecular‐Weight, Helically Chiral Polyquinoxaline‐Based Phosphines

N-Heterocyclic Pyridylmethylamines: Synthesis, Complexation, Molecular Structure, and Application to Asymmetric Suzuki–Miyaura and Oxidative Coupling Reactions

The synthesis of N,N-bidentate ligands based on a π-deficient N-heterocyclic pyridylmethylamine core is described. The preparation and characterization of the corresponding N,N-ligand–palladium complexes in solution and the solid state are illustrated. Pd complexes showed a good yield and moderate catalytic activity (up to 40% ee) in the asymmetric Suzuki–Miyaura coupling reaction, leading to methoxybinaphthyl derivatives. The combination of N,N-pyridylmethylamines with cuprous iodide revealed effective catalytic systems in oxidative naphthol derivative coupling reactions, affording the corresponding binaphthyls in high yields and with enantioselectivities of up to 61%.

Chiral Diene as the Ligand for the Synthesis of Axially Chiral Compounds via Palladium-Catalyzed Suzuki−Miyaura Coupling Reaction

The first palladium-diene-catalyzed asymmetric Suzuki-Miyaura coupling reaction has been achieved. A number of functionalized biaryls were obtained in high yields and in moderate to high enantioselectivities. The existence of an ortho-formyl group greatly improves the catalyst efficiency and permits further synthetic elaborations.

ChemInform Abstract: Asymmetric Suzuki—Miyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin.

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.

Asymmetric Suzuki-Miyaura Coupling in Water Using a Chiral Polymeric Pd Catalyst

Asymmetric Suzuki-Miyaura coupling in water with a novel recyclable palladium complex of a polymer-supported chiral imidazo­indole phosphine ligand was described. Thus, PS-PEG-supported imidazoindole dicyclohexyl­phosphine (PS-PEG-L*, 7) was prepared from PS-PEG-NH2 and compound 6. The reaction of 2-methyl-1-iodonaphthalene with 2-methylnaphthyl boronic acid was catalyzed by the amphiphilic polymeric PS-PEG-L*-Pd complex to give 2,2′-dimethyl-1,1′-binaphthyl in 95% yield with 94% ee (S). The catalyst PS-PEG-L*-Pd was recovered readily and reused four times with little loss of its catalytic activity and stereoselectivity.

Palladium-Catalyzed Asymmetric Suzuki-Miyaura Coupling in Water

The authors reported an asymmetric Suzuki-Miyaura coupling in water with a recyclable palladium complex of a chiral imidazoindole phosphine ligand supported on an amphiphilic PS-PEG resin. The cross-coupled products were obtained in high enantioselectivities and high yields. The catalyst was readily recovered and reused four times without significant loss of catalytic activity and stereoselectivity.

Asymmetric Suzuki–Miyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin

You oughta use water: Broad functional-group (FG) tolerance was observed for the title coupling of aryl halides (X = Cl, Br, I) and aryl boronic acids to give biaryl compounds with up to 94% ee. The chiral imidazoindole phosphine-palladium catalyst supported on an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin could be recycled readily.

Asymmetric Suzuki–Miyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin

AbstractAb ins Wasser: Eine Verträglichkeit mit vielfältigen funktionellen Gruppen (FG) zeigt die Titelreaktion, die durch Kupplung von Arylhalogeniden (X=Cl, Br, I) und Arylboronsäuren mit bis zu 94 % ee zu Biarylen führt. Der chirale, auf einem amphiphilen Polystyrol‐Poly(ethylenglycol)(PS‐PEG)‐Harz fixierte Imidazoindolphosphan‐Palladium‐Katalysator ließ sich leicht zurückgewinnen.magnified image

Synthesis and characterization of FePd magnetic nanoparticles modified with chiral BINAP ligand as a recoverable catalyst vehicle for the asymmetric coupling reaction

The initial thermal decomposition of iron carbonyl (Fe(CO)(5)), followed by reduction of palladium acetylacetonate (Pd(acac)(2)) produced FePd nanoparticles (NPs) with an Fe(x)O(y)-rich core and a Pd-rich shell. The as-synthesized NPs were subsequently treated with (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthene ((S)-BINAP) as a chiral modifier, which provides them with the optical activity to show a negative Cotton effect in the circular dichroism (CD) spectrum. Characterization by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), superconducting quantum interface device (SQUID) and X-ray absorption fine structure (XAFS) measurements was performed. The FePd NPs modified with (S)-BINAP had a mean diameter of ca. 5.6 nm, and exhibited superparamagnetic behavior at 300 K with zero remanence and coercivity. The FePd-(S)-BINAP was shown to catalyze the asymmetric Suzuki-Miyaura coupling reaction with easy recovery from the reaction mixture by applying an external magnet. The designed architecture enabled the powerful combination of two functionalities, magnetism that responds to a magnetic field for easy recycling, as well as an optically active catalytic center that promotes the asymmetric coupling reaction.