220466-27-3

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• 141-32-2 acrylic acid n-butyl ester 
• 86487-19-6 tributyl(4-(trifluoromethyl)phenyl)stannane 
• 228873-97-0 hydroxy(dimethyl)(4-trifluoromethylphenyl)silane 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 128796-39-4 4-trifluoromethylphenylboronic acid 
• 2991-42-6 4-trifluorophenylsulfonyl chloride 
• 127-19-5 N,N-dimethyl acetamide 
• 131211-27-3 di-1-adamantylphosphine 
• 2062-26-2 3-<4'-(trifluoromethyl)phenyl>-2-propenoic acid 
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• 1643-19-2 tetrabutylammomium bromide 
• 98-56-6 4-chlorobenzotrifluoride 
• 292638-85-8 acrylic acid methyl ester 
• 329-15-7 4-trifluoromethyl-phenyl acetyl chloride 

Relevant academic research and scientific papers

Chemical-Reductant-Free Electrochemical Deuteration Reaction using Deuterium Oxide

We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 percent and yields up to 91 percent in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O2 evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.

Synthesis and Characterization of C, C -Type Palladacycles and Their Catalytic Application in Mizoroki-Heck Coupling Reaction

Two series of ligand precursors, based on imidazo[1,2-a]pyridine and C2-phenyl substituted imidazole moieties, were developed and synthesized in high yields, featuring an N-CH2(C=O)Ar substituent on the imidazole ring. Upon reacting with palladium acetate, both series of ligands underwent double C-H bond activations at the methylene and o-aryl carbon sites on the N-CH2(C=O)Ar substituent, yielding C,C-type palladacycles bearing five-membered chelate rings. A dimeric palladium complex with bridging bromides was obtained from the ligand precursor with the bromide anion, whereas an ionic palladium complex with two "throw away" pyridine ligands was formed with the precursor of the tetrafluoroborate anion. All complexes are air-stable and were characterized by 1H and 13C NMR spectroscopy and elemental analysis. The structures of three of the new complexes were further established by single-crystal X-ray diffraction studies. These complexes have been screened for catalyzing Mizoroki-Heck coupling reaction using ionic salt as solvent. The complex based on imidazo[1,2-a]pyridine, which has an electron-donating 4-methoxyphenyl ring on the ligand scaffold, was the most efficient catalyst, capable of using activated aryl chloride and sterically hindered aryl bromide as substrates. It was also successfully applied in the green process of one-pot Mizoroki-Heck coupling/trans-esterification reaction in molten ionic salt.

Nickel nanoparticles supported on diphenylphosphinated poly(vinyl alcohol-co-ethylene) as a new heterogeneous and recyclable catalyst for Mizoroki–Heck reactions

Nickel nanoparticles (NiNPs) supported on diphenylphosphinated poly(vinyl alcohol-co-ethylene) (DPP-PVA-co-PE) were synthesised by first reacting poly(vinyl alcohol-co-ethylene) with chlorodiphenylphosphine (ClPPh2) under basic conditions and then treating the product with Ni(OAc)2 followed by reduction with NaBH4. (DPP-PVA-co-PE)-NiNPs, a new metallised polymer, was then shown to efficiently catalyse Mizoroki–Heck reactions of aryl iodides, bromides or activated chlorides with olefins such as styrene and n-butyl acrylate in dimethylformamide. In contrast with other polymer-supported catalysts, the main advantage of this method is the low cost of the catalyst due to the simple synthetic route using easily obtained materials and good recoverability. Transmission electron microscopy and X-ray diffraction measurements were used to show the high metal dispersion and small sizes of Ni nanoparticle on the surface of the modified polymer. DPP-PVA-co-PE-NiNPs could be recycled several times.

N-Acylsaccharins as Amide-Based Arylating Reagents via Chemoselective N-C Cleavage: Pd-Catalyzed Decarbonylative Heck Reaction

Palladium-catalyzed decarbonylative Heck reaction of amides by chemoselective N-C activation using N-acylsaccharins as coupling partners has been accomplished. These studies represent only the second example of amide-Heck reactions reported to date. A broad range of electronically diverse amide and olefin coupling partners is amenable to this transformation. Orthogonal site-selective Heck cross-couplings by C-Br/N-C cleavage and mechanistic studies are reported. This report introduces readily available, bench-stable, cheap, and benign N-acylsaccharins as aryl transfer reagents to access versatile aryl-metal intermediates.

Preparation and characterization of palladium nanoparticles supported on phosphinated poly(Vinyl Alcohol) as new recyclable catalyst and their application for heck cross-coupling reactions

Diphenylphosphinated poly(vinyl alcohols) (DPP-PVA) were synthesized by the insertion of chlorodiphenylphosphine to PVA in the presence of triethyl amine as base. The structure of this new polymer was confirmed by FT-IR and NMR spectroscopy. This polymer can be used as ligand for the preparation of nanoparticles of palladium. The complexation of PVA-grafted phosphinite with palladium(II) acetate was carried out to obtain the heterogeneous catalytic system. X-ray diffraction techniques, X-ray photoelectron spectroscopy, and transmission electron microscopy imaging revealed that palladium was dispersed into the nanometer scale through the support. This catalytic system showed excellent activity in the cross-coupling Heck reactions of olefinic compounds with aryl iodides, bromides as well as chlorides and gave high yields within short reaction times. Elemental analysis of Pd by the inductively coupled plasma technique on the supported catalyst exhibited low leaching of the metal into the solution. The catalyst can be reused several times in the repeated Heck reaction cycles without considerable loss in its activity.

2-Hydroxy-1,10-phenanthroline vs 1,10-Phenanthroline: Significant ligand acceleration effects in the Palladium-Catalyzed Oxidative Heck reaction of arenes

A series of bidentate monoanionic nitrogen ligands were designed and applied in the Pd-catalyzed oxidative Heck reaction of arenes with alkenes. Significant ligand-accelerated effects were observed, and direct C-H functionalized products were formed in high yields with meta-selectivity.

A palladium-nanoparticle and silicon-nanowire-array hybrid: A platform for catalytic heterogeneous reactions

We report the development of a silicon nanowire array-stabilized palladium nanoparticle catalyst, SiNA-Pd. Its use in the palladium-catalyzed Mizoroki-Heck reaction, the hydrogenation of an alkene, the hydrogenolysis of nitrobenzene, the hydrosilylation of an α,β-unsaturated ketone, and the C-H bond functionalization reactions of thiophenes and indoles achieved a quantitative production with high reusability. The catalytic activity reached several hundred-mol ppb of palladium, reaching a TON of 2 000 000. An array of reactions: A silicon-nanowire-array-stabilized palladium-nanoparticle catalyst, SiNA-Pd, was designed and used in the palladium-catalyzed Mizoroki-Heck reaction. It can catalyze a variety of other reactions and has a high reusability. Copyright

Copper-promoted sandmeyer trifluoromethylation reaction

A copper-promoted trifluoromethylation reaction of aromatic amines is described. This transformation proceeds smoothly under mild conditions and exhibits good tolerance of many synthetically relevant functional groups. It provides an alternative approach for the synthesis of trifluoromethylated arenes and heteroarenes. It also constitutes a new example of the Sandmeyer reaction.

An efficient palladium(II) catalyst for oxidative Heck-type reaction under base-free conditions

An efficient catalytic system for the palladium-catalyzed oxidative Heck reaction between arylboronic acids and various alkenes has been developed. Using the bis(aminoalkoxy)palladium complex of N,N-dimethylethanolamine as a catalyst, a series of substituted alkenes were obtained in moderate to excellent yields under mild reaction conditions. This protocol could be tolerated to arylboronic acids containing electron-donating or withdrawing groups and a wide range of olefins, such as acrylate, allyl esters, allyl ethers and alkenylphosphonate. A plausible reaction mechanism of the oxidative Heck reaction was proposed.

Pd-catalyzed sequential C-C bond formation and cleavage: Evidence for an unexpected generation of arylpalladium(II) species

A Pd(II)-catalyzed reaction engaging alkenyl β-keto esters is reported that leads to the formation of 1-naphthols and an unexpected generation of arylpalladium(II) species. Interception of the in situ generated arylpalladium(II) species in a Mizoroki-Heck reaction, together with additional mechanistic studies, provided strong evidence in support of the first aromatization-driven β-carbon elimination process. A single Pd catalyst served to promote a series of both C-C bond forming and cleavage events in an unprecedented manner.