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Relevant academic research and scientific papers

Activator-Promoted Aryl Halide-Dependent Chemoselective Buchwald-Hartwig and Suzuki-Miyaura Type Cross-Coupling Reactions

Herein, we report the development of aryl halide-dependent chemoselective reactions, viz., the Buchwald-Hartwig type coupling reaction of an aryl iodide with an arylboronic acid and an aryl amine in the presence of a heterogeneous and reusable nickel catalyst and the Suzuki-Miyaura type coupling of an aryl chloride under similar conditions. Control experiments revealed that the presence of stoichiometric amounts of the phenylboronic acid/ester and aryl amine are essential for both reactions. NMR and XAFS studies suggested the formation of a boron-amine "ate"complex.

Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids

The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.

Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles

A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.

Method for synthesizing diarylamine through N-arylation reaction of arylamine under copper catalysis

The invention provides a method for synthesizing diarylamine through an N-arylation reaction of arylamine under copper catalysis. The method comprises the following steps: S1, selecting a proper amount of a reaction reagent, a catalyst, a solvent and the like; S2, sequentially adding a reaction reagent, a catalyst, a solvent and the like into a reaction tube with a magnetic bar; S3, selecting a proper amount of AcOH, and adding the AcOH into the reaction tube; S4, heating the reaction tube; S5, performing oil bath treatment; S6, cooling to room temperature, and diluting; S7, extracting by using ethyl acetate; S8, washing the organic layer with saline water; S9, drying on anhydrous Na2SO4; S10, evaporating under vacuum; and S11, purifying the residues into the pure product through silica gel chromatography. A scheme that arylamine and an environmentally-friendly and stable aryl silicon reagent are subjected to an N-arylation reaction under the catalysis of a cheap copper reagent is provided, Cu(OAc)2 is used as a catalyst to react in DMSO in the atmosphere of O2, the conversion reactivity is good, the substrate range is wide, and the method has good tolerance to reaction substrates with various functional groups under mild reaction conditions.

Quantifying Through-Space Substituent Effects

The description of substituents as electron donating or withdrawing leads to a perceived dominance of through-bond influences. The situation is compounded by the challenge of separating through-bond and through-space contributions. Here, we probe the experimental significance of through-space substituent effects in molecular interactions and reaction kinetics. Conformational equilibrium constants were transposed onto the Hammett substituent constant scale revealing dominant through-space substituent effects that cannot be described in classic terms. For example, NO2 groups positioned over a biaryl bond exhibited similar influences as resonant electron donors. Meanwhile, the electro-enhancing influence of OMe/OH groups could be switched off or inverted by conformational twisting. 267 conformational equilibrium constants measured across eleven solvents were found to be better predictors of reaction kinetics than calculated electrostatic potentials, suggesting utility in other contexts and for benchmarking theoretical solvation models.

Synthesis and characterization of new square planar heteroleptic cationic complexes [Ni(ii) β-oxodithioester-dppe]+; Their use as a catalyst for Chan-Lam coupling

Novel heteroleptic [Ni(ii) β-oxodithioester-dppe]+PF6- complexes (β-oxodithioester = methyl-3-hydroxy-3-benzyl-2-propenedithioate L1 1, methyl-3-hydroxy-3-(p-methoxyphenyl)-2-propenedithioate L2 2, methyl-3-hydroxy-3-(naphthyl)-2-propenedithioate L3 3, methyl-3-hydroxy-3-(p-chlorophenyl)-2-propenedithioate L4 4, methyl-3-hydroxy-3-(p-bromophenyl)-2-propenedithioate L5 5 and methyl-3-hydroxy-3-(p-cyanophenyl)-2-propenedithioate L6 6) have been synthesized and characterized by elemental (C, H, N) analysis, ESI-MS, IR, UV-visible, 1H, 13C{1H}, 31P{1H} and 19F{1H} NMR spectroscopy. The distorted square planar structures of the isomorphous cationic complexes 2, 3, 4 and 5 have been determined by X-ray crystallography. The catalytic activities of 1-6 were investigated for the Chan-Lam coupling reaction involving arylboronic acids and amines to afford N-arylated products in good to excellent yields under mild conditions with 1 mol% catalyst loading. This catalytic protocol offers significant functional group tolerance, and is endowed with a broad substrate scope. This journal is

Well-Designed N-Heterocyclic Carbene Ligands for Palladium-Catalyzed Denitrative C-N Coupling of Nitroarenes with Amines

The C-N bond formation is one of the fundamental reactions in organic chemistry, because of the widespread presence of amine moieties in pharmaceuticals and biologically active compounds. Palladium-catalyzed C-N coupling of haloarenes represents one of the most efficient approaches to aromatic amines. Nitroarenes are ideal alternative electrophilic coupling partners, since they are inexpensive and readily available. The denitration and cross-coupling using nitroarenes as the electrophilic partners is challenging, because of the low reactivity of the Ar-NO2 bond toward oxidative addition. We report here the C-N coupling of nitroarenes and amines using palladium/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily available from commercial chemicals. The reaction shows broad substrate scope and functional group tolerance. The method is applicable to both aromatic and aliphatic amines, and many secondary and tertiary aromatic amines bearing various functional groups were obtained in high yields.

Method for catalyzing nitro-arene and amine compound to be synthesized into aromatic amine compounds through palladium/imidazolium salt

The invention discloses a method for catalyzing nitro-arene and an amine compound to be synthesized into aromatic amine through palladium/imidazolium salt. The method comprises the steps that in an organic solvent, the palladium/imidazolium salt is taken as a catalyst, the nitro-arene and the amine compound are subjected to a coupling reaction under the function of alkali, and then the aromatic amine compounds are obtained through aftertreatment. The method is simple in ligand synthesis, storage is facilitated, the price is low, the use quantity of ligands is low, the yield of the product is high, and the substrates have high applicability and are suitable for preparing diarylamine and N-alkylated arylamine. The method can be used for synthesizing a series of aromatic amine compounds, andthe aromatic amine compounds have high application value in the fields of pesticides, medicines, materials and the like.

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald–Hartwig Aminations

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII–NHO complexes have been formed and their use as pre-catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C?N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.

Copper-Catalyzed NaBAr 4-Based N-Arylation of Amines

Using NaBAr 4 as an arylating agent, the formation of carbon-heteroatom bonds by a Cham-Lam cross-coupling reaction in the presence of catalytic copper(II) acetate monohydrate in acetonitrile at room temperature under air is described. The investigation of reaction scope suggests that several aliphatic and aromatic amines are compatible. In particular, the reaction of alkylamine and NaBAr 4 proceeds smoothly to offer the corresponding products in good to excellent yields.