Cross-coupling Reactions Of Aryl Chlorides Research Articles

Stereospecific Cross-Coupling of Alkenylsilanolates with Aryl Chlorides

While the aryl-aryl cross-coupling reaction of aryl chlorides and arylboronic acids has become widely used, the same reaction of alkenylboronic acids is not as smooth, even in the presence of modern powerful catalysts, due to the intrinsically lower reactivity of these compounds. The use of alkenyl silanolates, which are stable, readily available crystalline compounds, is a good alternative, especially when a product with high stereoselectivity is required. The reactions between a broad variety of aryl or hetaryl chlorides and alkenyl silanolates lead to the cross-coupling products in excellent yields and stereoselectivities.

Highly Efficient and Functional‐Group‐Tolerant Catalysts for the Palladium‐Catalyzed Coupling of Aryl Chlorides with Thiols

The cross-coupling reaction of aryl chlorides with aliphatic and aromatic thiols catalyzed by palladium complexes of the strongly binding bisphosphine CyPF-tBu ligand (1) is reported. Most of the reactions catalyzed by complexes of ligand 1 occur with turnover numbers that exceed those of previous catalysts by two orders of magnitude. The reactions occur with excellent yields, broad scope and high tolerance of functional groups. Coupling of aryl halides with thiols in the presence of low loadings of catalysts derived from other Josiphos type ligands, as well as ligands of other structural types, are also described.

Triphenylphosphine as a Ligand for Room-Temperature Ni(0)-Catalyzed Cross-Coupling Reactions of Aryl Chlorides with Arylboronic Acids

Room-temperature Ni(0)-catalyzed cross-coupling reactions of deactivated aryl chlorides with arylboronic acids with inexpensive triphenylphosphine (PPh3) as a supporting ligand have been accomplished in good to excellent yields. Air-stable Ni(PPh3)2Cl2 has also been established as catalyst precursor, and highly active nickel catalysts were obtained when the reduction of Ni(PPh3)2Cl2 with n-BuLi was carried out in the presence of an aryl chloride.

Palladium Complexes Bearing Novel Strongly Bent Trans-Spanning Diphosphine Ligands: Synthesis, Characterization, and Catalytic Activity

The new air-stable chelating diphosphine ligands 1,8-bis(diisopropylphosphino)triptycene (2) and 1-(diisopropylphosphino)-8-(diphenylphosphino)triptycene (3) were synthesized in 51−73% yield from readily available starting materials. The examination of their coordination modes in the palladium(II) complexes [PdCl2(2)] (4) and [PdCl2(3)] (5) by means of 1H, 13C, and 31P NMR is consistent with the formation of trans-spanned complexes. X-ray analysis of 4 and 5 confirmed the structure but disclosed a strong distortion of the palladium centers from the expected square-planar geometry toward a butterfly-like environment. Further investigation revealed that 2 can also behave as a binucleating ligand, forming the quasi-closed halogen-bridged dipalladium complex 6, featuring an unusual nonplanar Pd2(μ-Cl)2Cl2 core. The catalytic activity of the new ligands and complexes was tested in palladium-catalyzed cross-coupling reactions of aryl chlorides with phenylboronic acid.

An efficient catalyst system for diaryl ether synthesis from aryl chlorides

The combination of 2-phosphino-substituted N-arylpyrroles or related indoles (cata CXium ®P) and Pd(OAc) 2 allows for efficient cross-coupling reactions of aryl chlorides and phenols to give diaryl ethers. A variety of aryl and heteroaryl chlorides can be coupled with substituted phenols showing unprecedented catalyst turnover numbers.

Sonogashira cross-coupling reactions of aryl chlorides with alkynes catalysed by a tetraphosphine–palladium catalyst

A range of aryl chlorides undergoes cross-couplings with alkynes in good yields in the presence of [PdCl(C 3H 5)] 2/ cis, cis, cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst. A variety of aryl chlorides such as chloroacetophenone, chlorobenzonitrile, chloronitrobenzene, chloroanisole or chlorotoluene have been used successfully. The reaction also tolerates several alkynes such as phenylacetylene, dec-1-yne, ethynylcyclohexene or alk-1-ynols. Furthermore, this catalyst can be used at low loading with some substrates.

Microwave‐Assisted Negishi and Kumada Cross‐Coupling Reactions of Aryl Chlorides.

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Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyltrimethoxysilane Catalyzed by Palladium-Phosphinous Acid Complexes.

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Microwave-assisted Negishi and Kumada cross-coupling reactions of aryl chlorides.

Rapid Pd or Ni-catalyzed microwave-accelerated Negishi and Kumada cross-coupling reactions of aryl chlorides in solution and on solid phase are reported.

A Highly Efficient Catalytic System for Cross‐Coupling of Aryl Chlorides and Bromides with Malononitrile Anion by Palladium Carbene Complexes.

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Macromolecular Effect: Synthesis of a Ferrocenylmethylphosphine‐Containing Polymer as Highly Efficient Ligands for Room‐Temperature Palladium(0)‐Catalyzed Suzuki Cross‐Coupling Reactions of Aryl Chlorides.

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Macromolecular effect: synthesis of a ferrocenylmethylphosphine-containing polymer as highly efficient ligands for room-temperature palladium(0)-catalyzed Suzuki cross-coupling reactions of aryl chlorides.

The design and synthesis of a ferrocenylmethylphosphine-containing polymer and its application as efficient ligands for the room-temperature Pd(0)-catalyzed cross-coupling reaction of aryl chlorides with arylboronic acids, for which corresponding monomeric monophosphines are totally inactive, are described. Our work demonstrated that rather small monophosphine moieties such as RPPh2 can be used as highly efficient ligands when appropriately incorporated into a rigid and sterically regular polymer network and using monophosphine-containing polymers as ligands is a feasible approach to access highly active (monophosphine)-palladium(0) complexes. The macromolecular approach described here may open a new avenue to other coordinatively unsaturated (monoligand)-transition metal complexes which are potentially useful in organic synthesis.

Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl­trimthoxysilane Catalyzed by Palladium-Phosphinous Acid Complexes

Three palladium-phosphinous acid complexes, POPd, POPd1, and POPd2, have been employed in cross-coupling reactions of aryl halides and phenyltrimethoxysilane activated by tetrabutylammonium fluoride. A variety of biaryls were prepared from aryl and hetaryl chlorides and bromides in good to high yields under mild reaction conditions. Bromides afford better results than their chloride analogs and acetonitrile was found to be a superior solvent over DMF, ethyl acetate, and isopropyl alcohol. This coupling procedure tolerates nitrile, ketone and ester groups and converts 4,7-dichloroquinoline to 7-chloro-4-phenylquinoline with high regioselectivity.

Highly active, air-stable versatile palladium catalysts for the C-C, C-N, and C-S bond formations via cross-coupling reactions of aryl chlorides.

Highly active, air-stable versatile palladium catalysts for the C-C, C-N, and C-S bond formations via cross-coupling reactions of aryl chlorides.

ChemInform Abstract: Efficient Cross-Coupling Reactions of Aryl Chlorides and Bromides with Phenyl- or Vinyltrimethoxysilane Mediated by a Palladium/Imidazolium Chloride System.

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Efficient cross-coupling reactions of aryl chlorides and bromides with phenyl- or vinyltrimethoxysilane mediated by a Palladium/Imidazolium chloride system

A combination of palladium acetate and the imidazolium salt IPr.HCl (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) has proven to be highly efficient in the cross coupling reactions of aryl bromides and electron-deficient aryl chlorides with phenyltrimethoxysilane or vinyltrimethoxysilane. The catalytic performance of this system was found to be comparable to that of systems using PCy(3) and P(o-tol)(3).

Palladium-bisimidazol-2-ylidene complexes as catalysts for general and efficient Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids

A series of bisimidazolium salts 1– 6 were synthesized and evaluated as precursors to bisimidazol-2-ylidene ligands in palladium-catalyzed Suzuki cross-coupling reactions with aryl chlorides and arylboronic acids. The bisimidazolium salt 6 was found to be superior over imidazolium and other bisimidazolium salts affording high yields of biaryl products employing a wide variety of substrates.

Palladium−Imidazol-2-ylidene Complexes as Catalysts for Facile and Efficient Suzuki Cross-Coupling Reactions of Aryl Chlorides with Arylboronic Acids

Palladium−Imidazol-2-ylidene Complexes as Catalysts for Facile and Efficient Suzuki Cross-Coupling Reactions of Aryl Chlorides with Arylboronic Acids

Suzuki-type coupling of chloroarenes with arylboronic acids catalysed by nickel complexes

A Suzuki-type cross-coupling reaction of aryl chlorides with arylboronic acids using nickel-catalysts is described. The best results were obtained at 95 °C in the presence of K 3PO 4 and in dioxane using Ni(dppf)Cl 2. Unsymmetrical biaryls with both electron-withdrawing and electron-donating functional groups were obtained in high yields.