102512-07-2

Upstream product

• 402-54-0 p-nitrobenzotrifluoride 
• 2043-61-0 cyclohexanecarbaldehyde 
• 34913-26-3 4-nitroso-1-(trifluoromethyl)benzene 

Downstream Products

• 1445871-90-8 C₁₈H₁₁F₈NO₂ 
• 1445871-76-0 N-(pentafluorobenzoyl)-N-(p-trifluoromethylphenyl)hydroxylamine 
• 88730-38-5 C₁₀H₁₀F₃NO₄S 
• 88730-43-2 N-Hydroxy-N-(4-trifluoromethyl-phenyl)-acetamide 
• 340283-83-2 α-(phenyl)-N-[4-(trifluoromethyl)phenyl]nitrone 
• 1377823-84-1 (R,Z)-N-((2,2-dimethyl-3-((2,4,6-triisopropylphenyl)sulfonyl)oxazolidin-4-yl)methylene)-4-(trifluoromethyl)aniline oxide 

Relevant academic research and scientific papers

Asymmetric Synthesis of α-Alkylidene-β-Lactams through Copper Catalysis with a Prolinol-Phosphine Chiral Ligand

A copper/prolinol-phosphine chiral catalyst enabled the one-step synthesis of chiral α-alkylidene-β-lactams. Optimization of the chiral ligand for steric and electronic properties realized the highly enantioselective coupling of nitrones and propargyl alcohol derived alkynes. The resulting chiral α-alkylidene-β-lactams served as a platform for various β-lactams via well-established transformations of α,β-unsaturated carbonyl compounds.

Hydroxamic Acids as Chemoselective (ortho-Amino)arylation Reagents via Sigmatropic Rearrangement

The use of readily available hydroxamic acids as reagents for the chemoselective (ortho-amino)arylation of amides is described. This reaction proceeds under metal-free, mild conditions, displays a very broad scope, and constitutes a direct approach for the metal-free attachment of aniline residues to carbonyl derivatives.

Practical bromination of arylhydroxylamines with SOBr2 towards ortho-bromo-anilides

A facile approach for synthesizing ortho-bromoanilides from readily available aryhydroxylamines and thionyl bromide is demonstrated in this work. Mild reaction conditions and broad scope of substrates ranging from heterocyclic structures to pharmaceutics-potential motifs are used in the reactions of this paper. Efficient bromination of ortho C–H bonds of the aryhydroxylamines has been achieved. Ortho-bromoanilide products were obtained in good to excellent yields, and model scaled-up reactions of this synthetic approach are shown in this work.

Highly Selective and Solvent-Dependent Reduction of Nitrobenzene to N-Phenylhydroxylamine, Azoxybenzene, and Aniline Catalyzed by Phosphino-Modified Polymer Immobilized Ionic Liquid-Stabilized AuNPs

Gold nanoparticles stabilized by phosphine-decorated polymer immobilized ionic liquids (AuNP@PPh2-PIILP) is an extremely efficient multiproduct selective catalyst for the sodium borohydride-mediated reduction of nitrobenzene giving N-phenylhydroxylamine, azoxybenzene, or aniline as the sole product under mild conditions and a very low catalyst loading. The use of a single nanoparticle-based catalyst for the partial and complete reduction of nitroarenes to afford three different products with exceptionally high selectivities is unprecedented. Under optimum conditions, thermodynamically unfavorable N-phenylhydroxylamine can be obtained as the sole product in near quantitative yield in water, whereas a change in reaction solvent to ethanol results in a dramatic switch in selectivity to afford azoxybenzene. The key to obtaining such a high selectivity for N-phenylhydroxylamine is the use of a nitrogen atmosphere at room temperature as reactions conducted under an inert atmosphere occur via the direct pathway and are essentially irreversible, while reactions in air afford significant amounts of azoxy-based products by virtue of competing condensation due to reversible formation of N-phenylhydroxylamine. Ultimately, aniline can also be obtained quantitatively and selectively by adjusting the reaction temperature and time accordingly. Introduction of PEG onto the polyionic liquid resulted in a dramatic improvement in catalyst efficiency such that N-phenylhydroxylamine could be obtained with a turnover number (TON) of 100000 (turnover frequency (TOF) of 73000 h-1, with >99% selectivity), azoxybenzene with a TON of 55000 (TOF of 37000 h-1 with 100% selectivity), and aniline with a TON of 500000 (TOF of 62500 h-1, with 100% selectivity). As the combination of ionic liquid and phosphine is required to achieve high activity and selectivity, further studies are currently underway to explore whether interfacial electronic effects influence adsorption and thereby selectivity and whether channeling of the substrate by the electrostatic potential around the AuNPs is responsible for the high activity. This is the first report of a AuNP-based system that can selectively reduce nitroarenes to either of two synthetically important intermediates as well as aniline and, in this regard, is an exciting discovery that will form the basis to develop a continuous flow process enabling facile scale-up.

An asymmetric pericyclic cascade approach to 3-alkyl-3-aryloxindoles: Generality, applications and mechanistic investigations

The reaction of L-serine derived N-arylnitrones with alkylarylketenes generates asymmetric 3-alkyl-3-aryloxindoles in good to excellent yields (up to 93%) and excellent enantioselectivity (up to 98% ee) via a pericyclic cascade process. The optimization, scope and applications of this transformation are reported, alongside further synthetic and computational investigations. The preparation of the enantiomer of a Roche anti-cancer agent (RO4999200) 1 (96% ee) in three steps demonstrates the potential utility of this methodology.

Interrupted fischer-indole intermediates via oxyarylation of alkenyl boronic acids

The oxyarylation of alkenyl boronic acids with N-arylbenzhydroxamic acids has been achieved under both copper-mediated and copper-catalyzed conditions to provide access to interrupted Fischer-indole intermediates. This transformation is believed to proceed through a copper-promoted C-O bond forming event followed by a [3,3] rearrangement. The scope of the method is described and mechanistic experiments are discussed.

Asymmetric pericyclic cascade approach to spirocyclic oxindoles

The reaction of chiral N-arylnitrones with carbocyclic alkylarylketenes generates spirocyclic oxindoles in good yields and with excellent levels of enantioselectivity (90-99% ee) via a pericyclic cascade process.

para-Substituted N-Nitroso-N-oxybenzenamine ammonium salts: A new class of redox-sensitive nitric oxide releasing compounds

N-Nitroso-N-oxybenzenamine ammonium salts with -OMe, -Me, -H, -F, -Cl, - CF3, and -SO2Me substituents at the para position of the phenyl ring constitute a new class of-redox sensitive nitric oxide (NO) releasing compounds. These compounds yield nitric oxide and the corresponding nitrosobenzene derivatives by a spontaneous dissociation mechanism after undergoing a one electron oxidation. Oxidation of these compounds can be achieved through chemical, electrochemical and enzymatic methods. It was observed electrochemically that the amount of NO generated was dependent on the substituent effect and the applied oxidation potential. Electron- withdrawing substituents increase the oxidation potential of the compound. A linear correlation was observed when the peak potentials for the oxidation were graphed versus the Hammett substituent constant. Density functional theory calculations were also performed on this series of compounds. The theoretical oxidation energies of the corresponding anions show a strong linear correlation with the experimental potentials. Furthermore, enzymatic oxidation using horseradish peroxidase showed a similar substituent effect. These results indicate that substitution at the para position of the phenyl ring has a profound effect on the stability, oxidation potential and enzymatic kinetic properties of the compounds. Thus para-substituted N- nitroso-N-oxybenzenamine salts comprise a new class of redox-sensitive nitric oxide releasing agents. (C) 2000 Elsevier Science Ltd.

ACID CATALYZED REDUCTION OF NITROSOBENZENE IN WATER BY 1-BENZYL-3,5-DIPYRROLIDINOCARBAMOYL-1,4-DIHYDROPYRIDINE AS A NADH ANALOG

Acid catalysis has been observed for the reduction of substituted nitrosobenzenes in water by an acid stable NADH analog, 1-benzyl-3,5-dipyrrolidinocarbamoyl-1,4-dihydropyridine.