34160-14-0

Upstream product

• 615-37-2 ortho-methylphenyl iodide 
• 624-31-7 4-tolyl iodide 
• 2101-86-2 p-methylazidobenzene 
• 108-88-3 toluene 
• 95-53-4 o-toluidine 
• 623-10-9 N-(4-methylphenyl)hydroxylamine 
• 15999-95-8 4-methylphenylbenzimidoyl chloride 
• 106-49-0 p-toluidine 
• 95-46-5 2-methylphenyl bromide 
• 589-92-4 1-methylcyclohexan-4-one 
• 106-38-7 para-bromotoluene 
• 585526-04-1 N-(4-methoxy-4-methylcyclohexa-2,5-dien-1-ylidene)-4-methylbenzenesulfonamide 
• 73774-44-4 bis(2-methylphenyl)borinic acid 
• 88-72-2 1-methyl-2-nitrobenzene 

Downstream Products

• 613-15-0 2-methylacridine 
• 79365-09-6 2-methyl-9,10-dihydroacridine 

Relevant academic research and scientific papers

Improved Buchwald-Hartwig Amination by the Use of Lipids and Lipid Impurities

The development of green Buchwald-Hartwig aminations has long been considered challenging, due to the high sensitivity of the reaction to the environment. Here we show that food-grade and waste vegetable oils, triglycerides originating from animals, and natural waxes can serve as excellent green solvents for Buchwald-Hartwig amination. We further demonstrate that amphiphiles and trace ingredients present in triglycerides as additives have a decisive effect on the yields of Buchwald-Hartwig aminations.

Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application

Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.

Benzylic C?H Functionalisation by [Et3SiH+KOtBu] leads to Radical Rearrangements in o-tolyl Aryl Ethers, Amines and Sulfides

Reaction of Et3SiH+KOtBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).

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.

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.

Direct Synthesis of Diphenylamines from Phenols and Ammonium Formate Catalyzed by Palladium

Arylamines are commercially and synthetically useful compounds with a wide variety of applications. Their preparation has been traditionally achieved using metal-catalyzed C?N coupling reactions with aryl halides. In this work, 17 different diarylamines are prepared from phenols by using ammonium formate as the aminating reagent. Phenolic compounds are more desirable feedstocks, owing to their availability from lignin, making them valuable biorenewable alternatives to aryl halides. Ammonium formate is found to be a convenient surrogate for ammonia and a useful aminating reagent for phenols. Diarylamine products are obtained in good to excellent yields while only water and CO2 are generated as byproducts of the transformation.

Iodine-catalyzed synthesis of N, N ′-diaryl-o-phenylenediamines from cyclohexanones and anilines using DMSO and O2 as oxidants

A novel I2-catalyzed cross-dehydrogenative aromatization of cyclohexanones and anilines to synthesize N,N′-diaryl-o-phenylenediamines has been unprecedentedly developed with dimethyl sulfoxide and oxygen employed as mild terminal oxidants. To prove the rationality of the two separate dehydration steps of the proposed mechanism, a resulting I2-catalyzed cross-dehydrogenative aromatization of cyclohexenones and anilines to synthesize diarylamines has also been reported.

Synthesis of N-heterocyclic carbene-Pd(II) complexes and their catalytic activity in the Buchwald-Hartwig amination of aryl chlorides

Novel N-heterocyclic carbene-palladium(II) complexes using 2-picolinic acid as the ancillary ligand have been successfully developed under mild conditions. Their catalytic activity in organic synthesis has been initially tested in the Buchwald-Hartwig amination of secondary and primary amines with aryl chlorides. Various substituents on both substrates can be tolerated, giving the desired coupling products in good to almost quantitative yields. The minimum catalyst loading can be 0.01 mol%, implying their potential application toward industrial processes.

Organonickel complexes encumbering bis-imidazolylidene carbene ligands: Synthesis, X-ray structure and catalytic insights on Buchwald-Hartwig amination reactions

New four coordinated homoleptic bis(diimidazolylidene)nickel(II) complexes (C1 & C2) were synthesized and characterized by elemental analysis, NMR (1H and13C) as well as ESI-Mass spectrometry. The molecular structure of the complex C1 was identified by means of single-crystal X-ray diffraction analysis, which revealed that the complexes possess a distorted square planar geometry with chelating bis(diimidazolylidene) NHC ligands and two non coordinating bromide counter ions in tetradentate C4fashion. A survey of their catalytic activity in Buchwald?Hartwig amination has been performed. The newly synthesized complexes also catalyzed the amination of aryl chlorides in the presence of KOtBu. Various aryl chlorides and amines can react smoothly to give the corresponding aminated products in moderate to high yields. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine and quinoline derivatives. Both secondary and primary amines are well tolerated under the optimal reaction conditions.

N-heterocyclic carbene-palladium complex, and preparation method and application thereof

The invention discloses an N-heterocyclic carbene-palladium complex, and a preparation method and application thereof. The N-heterocyclic carbene-palladium complex disclosed by the invention is shown in Formula (I), wherein L1 is a quinoline ligand or isoquinoline ligand, and N in the L1 is connected with Pd; L2 is an N-heterocyclic carbene ligand, and carbene carbon in the L2 is connected with the Pd; and X1 and X2 are respectively independently an anionic ligand. The N-heterocyclic carbene-palladium complex disclosed by the invention can efficiently catalyze carbon-carbon or carbon-heteroatom coupling reaction using aryl halide as a substrate. The formula is shown in the specification.