Cross-coupling Reaction Of Arylboronic Acids Research Articles

Accessing aryl azidesviacopper powder-catalyzed cross-coupling of arylboronic acids with the hypervalent azido-iodine reagent ABZ(I)

The cross-coupling reaction of arylboronic acids with the hypervalent azido-iodine reagent ABZ(I) in the presence of a catalytic amount of copper powder under LED irradiation was found to give aryl azides in high yields.

Chemically Modified Chitosan Supports for Phosphine-free Pd-catalyzed Crosscoupling Reaction of Arylboronic Acids with Acid Chlorides

Backgroung:Phosphine-free Pd-catalytic platforms, i) combination with chitosan- Schiff base (CS-Py/Pd), ii) immobilized on chitosan-Schiff base (CS-Py@Pd), and iii) anchored to modified carbon nanotube support (CNT@CS-Py@Pd),Methods:They were evaluated regarding a novel pathway for the cross-coupling reaction of arylboronic acids with acid chlorides.Results:The CS-Py@Pd platform had the highest catalytic efficiency of the three platforms, yielding moderate to excellent yields of diaryl ketones.Conclusion:The catalytic activity of the Pd-catalyst was highly dependent upon the manufacturing process and type of support.

Ferrocenylated imine- and amine(secondary/tertiary)- phosphine P^N ligands and their Pd(II) complexes: Synthesis and structural characterization

A new family of ferrocenylated P^N ligands where the nitrogen donor is either of an imine or amine (secondary/tertiary), was synthesized. The condensation reaction between diphenylphosphino propylamine and formyl ferrocene led to the formation of imine ligand [(η5-C5H5)Fe{(η5-C5H4)CH=N-(CH2)3-PPh2)}] (1), which on reduction with NaBH4 gave secondary amine ligand [(η5-C5H5)Fe{(η5-C5H4)CH2-NH-(CH2)3-PPh2)}] (2). Additionally, nucleophilic substitution reaction of diphenylphosphino ethyl/propyl amine with [FcCH2NMe3+][I−] salt leads to tertiary-amine ligand [(η5-C5H5)Fe(η5-C5H4)CH2]2-N-(R-PPh2) where R= C2H4 (3) and C3H6 (4). The newly synthesized ferrocenylated ligands were then complexed with Pd(II) giving [cis(κ2-P^N)PdCl2] type complexes (5-8), where imine, secondary amine, and tertiary amine ligands act as a bidentate ligand. The molecular structures of ligand (3), and complexes (5), (6), and (7) have also been determined by X-ray crystallography. In the molecular structures of these complexes, the Pd(II) center presents a distorted square-planar geometry. During the isolation of ligand (4), corresponding phosphine oxide (4A) along with a phosphonium salt (4B) was also isolated as by-products and were characterized by X-ray crystallography. The preliminary catalytic evaluation of complex (7) in the Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl bromides was performed.

In situ palladium/N-heterocyclic carbene complex catalyzed carbonylative cross-coupling reactions of arylboronic acids with 2-bromopyridine under CO pressure: efficient synthesis of unsymmetrical arylpyridine ketones and their antimicrobial activities

The carbonylative Suzuki cross-coupling of 2-bromopyridine with various boronic acids to prepare unsymmetrical arylpyridine ketones has been carried out using palladium/N-heterocyclic carbene complexes as catalysts prepared in situ. The selectivity and the rate of these reactions are highly dependent on the conditions, i.e., nature of the palladium catalyst precursor, solvent, temperature and CO pressure. The main side-products arise from direct, non-carbonylative cross-coupling. Under the optimum conditions, arylpyridine ketones are recovered in high yields (60–88%). The antibacterial activities of the corresponding benzimidazole salts 2 were tested against Gram positive and negative bacteria using the agar dilution procedure, and their IC50 values have been determined.

Synthesis and palladium(II) metal chemistry of thiazoline/imidazoline derived ligands: An efficient catalyst for cross-coupling reactions of arylboronic acids with acid chlorides and aryl halides

The synthesis, reactivity, spectroscopic characterization and catalytic activities of a series of Pd(II) complexes bearing the chelating ligands 2-(4,5-dihydrothiazol-2-yl)aniline (2) and 2-(4,5-dihydro-1H-imidazol-2-yl)aniline (3) are reported. The reactions of 2 with [Pd(COD)Cl2] in 1:1 and 1:2 (ligand into metal and metal into ligand) molar ratios afforded the mononuclear complexes, PdCl2{κ2−N,S − 2−(4,5-dihydrothiazol-2-yl)aniline} (4), Pd{κ2−N,N’−2−(4,5-dihydrothiazol-2-yl)aniline}2 (5) and Pd{κ12−N,N’−κ22−N,S − 2−(4,5-dihydrothiazol-2-yl)aniline}2 (6), respectively, in good yields. The neutral mononuclear palladium complexes PdCl2{κ2−N,N’−(4,5-dihydro-1H-imidazol-2-yl)aniline} (7) and Pd{κ2−N,N’−2−(4,5-dihydro-1H-imidazol-2-yl)aniline}2 (8) were synthesized using [Pd(COD)Cl2] with appropriate molar ratios. The palladium complexes 4–8 were evaluated for their catalytic activities in base assisted cross coupling reactions between acid chlorides and aryl halide with boronic acids. The complex 4 was found to be an efficient catalyst for producing unsymmetrical ketones (TOF = 19.8 min−1) while complex 7 was effective for making biaryls (TOF = 19.8 min−1).

A thiosemicarbazone–palladium(II)–imidazole complex as an efficient pre-catalyst for Suzuki–Miyaura cross-coupling reactions at room temperature in aqueous media

A Pd(II) complex of two sterically crowded ligands, specifically an N,S-donor thiosemicarbazone and an N-donor imidazole, has been synthesized and characterized by physicochemical and spectroscopic methods. X-ray single-crystal analysis revealed that the coordination geometry around the palladium center is distorted square planar, and the chloride ligand is involved in intermolecular bifurcated X–H···Y-type (where X = C, N and Y = Cl) hydrogen bonding. This complex proved to be a highly active and retrievable pre-catalyst for additive-free Suzuki–Miyaura cross-coupling reactions of arylboronic acids with aryl bromides or chlorides at room temperature and 60 °C, respectively. The reactions require a low catalyst loading and the complex is converted to ~1.5–2.0 nm-sized Pd nanoparticles (probably the real catalyst). The catalyst can be reused up to seven times without significant loss in activity. Since the reaction proceeds under mild conditions in aqueous medium and the catalyst is recoverable, it provides an environmentally benign alternative to the existing protocols for Suzuki–Miyaura reactions. Biaryls can be synthesized in high yield under greener reaction conditions in the presence of efficient pre-catalyst, thiosemicarbazone–palladium(II)–imidazole.

N,N′-Bisaryl Substituted Chiral Linker-Bridged Bis(N-Heterocyclic Carbene) Palladium Complexes: Design, Synthesis, and Catalytic Properties

A series of novel N,N′-bisaryl bis(NHC) (NHC = N-heterocyclic carbene) precursors 5a–e, 12a–d, and 13a–c and their palladium complexes 14a–e, 15a–d, and 16a,b with (1R,2R)-cyclohexene and (1R,2R)-diphenylethylene linkers have been designed, synthesized in good yields, and fully characterized by NMR, HRMS, and elemental analysis. The X-ray single crystal analysis of 15a showed that these complexes adopted a slightly distorted square-planar geometry around the Pd(II) center. These N,N′-bisaryl-bis(NHC)-Pd complexes exhibit excellent catalytic activity in asymmetric aryl–aryl cross-coupling reactions of arylboronic acids and aryl halides. The axial chiral biaryl compounds could be achieved in high yields (up to 74%) and good enantioselectivities (up to 60% ee) within 24 h. The results show that for this kind of bis(NHC) palladium catalysts the structure characteristics of the chiral linkers have decisive effect on the enantioselectivities of cross-coupling reactions.

Eco-friendly Suzuki–Miyaura coupling of arylboronic acids to aromatic ketones catalyzed by the oxime-palladacycle in biosolvent 2-MeTHF

Oxime-palladacycle catalyzed aerobic cross-coupling reaction of arylboronic acids and acyl chlorides to yield aryl ketones was developed. The reaction proceeds efficiently in 2-MeTHF, which is derived from corncobs, sugar cane, and fulfils the 3rd, 5th and 7th principles of Green Chemistry.

N-(Pyridin-2-yl)benzamide: efficient ligand for the nickel catalyzed Chan–Lam cross-coupling reaction

An efficient protocol for the Chan–Lam cross-coupling reactions of arylboronic acids with aryl or alkyl amines has been developed by employing simple N-(pyridin-2-yl)benzamide ligand with Ni(OAc)2·4H2O in the presence of TMG base. The reaction proceeded well with high yields by employing various N-nucleophiles at low catalytic loadings.

A palladium–phosphine catalytic system as an active and recycable precatalyst for Suzuki coupling in water

The Suzuki–Miyaura reaction of various aryl halides with aryl boronic acids using {[Ph2PCH2PPh2CH=C(O)(C10H7)]PdCl2} as a catalyst has been investigated. The X-ray crystal structure of the catalyst reveals a five-membered chelate ring formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal center. This palladacycle exhibited excellent activities and reusability in the aqueous phase for the Suzuki cross-coupling reactions of arylboronic acids with aryl halides. The proposed protocol featured mild reaction conditions and notable simplicity and efficiency using Cs2CO3 as a base in water. The catalytic system could be reused four times without significant loss of activity.

Nickel(II) thiolates derived from transmetallation reaction of [Zn(Tab)4](PF6)2 with Ni(II) ions and their catalytic activity toward the C[sbnd]N coupling reactions

Reactions of NiCl2·6H2O or Ni(ClO4)2·6H2O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab)4](PF6)2 (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)4Ni3(μ-Tab)4]Cl0.5(PF6)5.5 (2), one mononuclear cationic complex [Ni(Tab)2(dppe)](PF6)2 (3), and one dinuclear cationic complex [Ni2(dppb)(μ-Tab)2(Tab)2](PF6)2(ClO4)2 (4). Complexes 2–4 were characterized by elemental analysis, IR, UV–vis, 1H and 31P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)4Ni3(μ-Tab)4]6+ hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)2]2+ fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]2+ species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2–4 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.

Building block synthesis of predominantly (E) symmetrical and unsymmetrical 1,2-difluorostilbenes from 1,2-dibromo-1,2-difluoroethene

An efficient synthesis of predominantly (E) symmetrical or unsymmetrical 1,2-difluorostilbenes based on the Suzuki–Miyaura palladium-catalyzed cross-coupling reaction of arylboronic acids with predominantly (E)-1,2-dibromo-1,2-difluoroethene in the presence of Cs2CO3 in toluene is described. The reaction preserved the stereochemistry of the building block and performed in good yield independently of the electron-withdrawing or electron-donating character of the substituents.

Synthesis of Aryl Thiocyanates via Copper-Catalyzed Aerobic Oxidative Cross-Coupling between Arylboronic Acids and KSCN

A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at <i>ortho</i> position, were suitable under the reaction conditions.

Correction to “Uncovering the Mechanism of the Ag(I)/Persulfate-Catalyzed Cross-Coupling Reaction of Arylboronic Acids and Heteroarenes”

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionCorrection to “Uncovering the Mechanism of the Ag(I)/Persulfate-Catalyzed Cross-Coupling Reaction of Arylboronic Acids and Heteroarenes”Niki R. Patel and Robert A. Flowers, II*Cite this: J. Am. Chem. Soc. 2013, 135, 20, 7788Publication Date (Web):May 7, 2013Publication History Published online7 May 2013Published inissue 22 May 2013https://doi.org/10.1021/ja402937cCopyright © 2013 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views1154Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (133 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Addition reactions,Cross coupling reaction,Deactivation,Order Get e-Alerts

An efficient synthesis of (Z)-α-fluorochalcones via the palladium-catalyzed cross-coupling reaction of (Z)-α-fluorocinnamoyl chloride with boronic acids

An efficient synthesis of α-fluorochalcones (1,3-diphenyl-2-fluoroprop-2-en-1-one) based on the Suzuki–Miyaura palladium-catalyzed cross-coupling reaction of arylboronic acids with α-fluorocinnamoyl chlorides in the presence of Cs2CO3 in toluene is described. This approach allows the synthesis of fluorinated analogues of functionalized natural chalcones.

Palladacycle-catalyzed cross-coupling reactions of arylboronic acids with carboxylic anhydrides or acyl chlorides

The triphenylphosphine–cyclopalladated ferrocenylimine (Cat. 2) exhibited highly catalytic activity for the both of arylboronic acids with carboxylic anhydrides and acyl chlorides with low catalyst loading (0.5 mol %). The reactions were unaffected by the presence of electron-releasing and electron-withdrawing substituents in both the arylboronic acids and carboxylic derivatives. Up to 98% yield was obtained for 32 examples. However, they were limited for arylboronic acid with strong electron-withdrawing groups. It is noting that catalyst 2 can be reused for eight times without losing its catalytic activity.

Mixed-donor N,N,O-tridentate ligands for palladium-catalyzed Suzuki reactions

Efficient Suzuki–Miyaura cross-coupling reactions of arylboronic acids with aryl halides catalyzed by Pd/N,N,O-tridentate ligands, using methanol as solvent and K3PO4 as base, afforded the corresponding cross-coupled biaryls in good to excellent yields. The Pd(OAc)2/N,N,O-tridentate ligands system was found to be very efficient for Suzuki reactions involving aryl bromides and activated aryl chlorides with arylboronic acid in methanol with K3PO4 as a base at 80 °C for 3 h. The mechanism of the Suzuki reactions along with the Suzuki-type self-coupling reaction catalyzed by these catalyst systems also proposed.

An Improvement of Nickel Catalyst for Cross-coupling Reaction of Arylboronic Acids with Aryl Carbonates by Using a Ferrocenyl Bisphosphine Ligand

Abstract Aryl carbonates work as electrophilic substrates for the Suzuki–Miyaura reaction in the presence of the nickel catalyst, which is generated from [Ni(cod)2] and ferrocenyl bisphosphine, DCyPF. The nickel catalyst allowed the cross-coupling reaction of arylboronic acids with non-benzo-fused aryl carbonates as well as naphthyl substrates.

Facile synthesis of substituted alkynes by nano-palladium catalyzed oxidative cross-coupling reaction of arylboronic acids with terminal alkynes

The oxidative cross-coupling of terminal alkynes with arylboronic acids catalyzed by the porous palladium nanospheres was developed. In the presence of silver oxide, triphenylphosphine and cesium carbonate, the reaction provided the corresponding arylalkynes with good to excellent yields. There were also other obvious advantages such as broad applicability, high selectivity, simple experimental operation as well as the convenient preparation, high efficiency and reusability of catalyst. The possible mechanism of this transition-metal nanoparticles catalyzed oxidative cross-coupling reaction of two nucleophiles was proposed.

Palladium-Catalyzed Oxidative Cross-Coupling Reaction of Arylboronic Acids with Diazoesters for Stereoselective Synthesis of (E)-α,β-Diarylacrylates

A Pd-catalyzed oxidative cross-coupling reaction of arylboronic acids with α-diazoesters was achieved using molecular oxygen as the sole reoxidant, and E-α,β-diarylacrylates were obtained in good yields and >20:1 E-to-Z selectivity.