19029-47-1

Upstream product

• 60-29-7 diethyl ether 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 586-96-9 Nitrosobenzene 
• 62-53-3 aniline 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 98-95-3 nitrobenzene 
• 100-65-2 N-Phenylhydroxylamine 

Downstream Products

• 100368-72-7 4-anilino-2,3-dimethyl-but-2-en-1-ol 
• 55110-59-3 3,4-dimethyl-1-phenyl-2,5-dihydro-pyrrole 
• 4533-41-9 N-phenyl-3,4-dimethylpyrrole 
• 131731-87-8 1,3,4-trimethyl-1-phenyl-2,5-dihydro-pyrrolium; bromide 
• 131732-51-9 1,3,4-trimethyl-1-phenyl-2,5-dihydro-pyrrolium; iodide 

Relevant academic research and scientific papers

Regioselective Allylic Amination Catalyzed by Iron Salts

Alkenes react with phenylhydroxylamine in the presence of Fe(II) and Fe(III) salts to produce N-phenyl-N-allyl amines in moderate to good yields.Unsymmetrical substrates react with high regioselectivity giving the products of double bond transition.

Molybdenum-catalysed allylic animation of alkenes by arylamine-ButOOH

Molybdenum peroxo complexes catalyse the regioselective allylic amination of alkenes by aryl amines with tert-butyl hydroperoxide as oxidant.

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.

Synthesis of 3,6-Dihydro-2H-[1, 2]-Oxazines from Nitroarenes and Conjugated Dienes, Catalyzed by Palladium/Phenanthroline Complexes and Employing Phenyl Formate as a CO Surrogate

Palladium/phenanthroline catalyzed reduction of nitroarenes by in situ-generated carbon monoxide, from the decomposition of phenyl formate, affords the corresponding nitrosoarenes. The latter are trapped by conjugated dienes to give the corresponding 3,6-dihydro-2H-[1, 2]-oxazines (hetero Diels-Alder adducts). Many functional groups are well tolerated. Yields are higher than those obtainable by any previously reported method, including the direct reaction of the diene with the pure nitrosoarene. The reaction can be performed in a single standard glass pressure tube, without the need for autoclaves or high-pressure CO lines.

Copper-catalyzed pyrrole synthesis from 3,6-dihydro-1,2-oxazines

Highly-functionalized pyrroles could be effectively synthesized from 3,6-dihydro-1,2-oxazines using a heterogeneous copper on carbon (Cu/C) under neat heating conditions. Furthermore, the in situ formation of 3,6-dihydro-1,2-oxazines via the hetero Diels-Alder reaction between nitroso dienophiles and 1,3-dienes and the following Cu/C-catalyzed pyrrole synthesis also provided the corresponding pyrrole derivatives in a one-pot manner.

Iron-catalyzed allylic C-H amination of substituted 1,3-dienes

A catalytic method for the selective allylic C-H amination of dienes and trienes using arylhydroxylamines has been developed. This iron-catalyzed approach involves the in situ generation of activated nitrosoarenes, which in turn react with dienes or trienes to give the corresponding aminomethyl dienes or trienes as the major products, and hetero-Diels-Alder adducts as minor products. The selectivity depends on the structures of both the catalyst and the substrate. We have also studied substituent effects using p-substituted phenylhydroxylamines. Copyright

In situ generation of nitroso compounds from catalytic hydrogen peroxide oxidation of primary aromatic amines and their one-pot use in hetero-Diels-Alder reactions

A method for in situ generation of nitroso compounds from organoselenium-catalyzed oxidation of anilines by hydrogen peroxide was developed. The generated nitroso compounds were subsequently used in hetero-Diels-Alder reactions. A variety of oxazines were synthesized in reasonable to good yields by this one-pot procedure using primary aromatic amines with different substituents and various conjugated dienes. This strategy might facilitate the current methodologies for nitroso chemistry since no isolation or purification of the nitroso compounds is required. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

A highly active catalyst for the reductive cyclization of ortho-nitrostyrenes under mild conditions

A mild and efficient method for the palladium-catalyzed reductive cyclization of ortho-nitrostyrenes to afford indoles is reported. Treatment of ortho-nitrostyrenes with 0.1 mol% palladium (II) trifluoroacetate [Pd(TFA) 2] and 0.7 mol% 3,4,7,8-tetramethyl-1,10-phenanthroline (tm-phen) in DMF at 15 psig CO and 80°C afforded indoles in good to excellent yields. When the reaction was conducted in toluene, the corresponding N-hydroxyindole was isolated. A mechanism that accounts for the formation of N-hydroxyindole is proposed.

Cyclopentadienyliron complexes of nitrosobenzene: Preparation, structure and reactivity with olefins

The preparation, characterization and reactivity of (η5- cyclopentadienyl)iron complexes of nitrosobenzene are investigated as potential intermediates in the [CpFe(CO)2]2 (1)-catalyzed allylic amination of olefins by nitro

Synthesis of oxazines and N-arylpyrroles by reaction of unfunctionalized dienes with nitroarenes and carbon monoxide, catalyzed by palladium-phenanthroline complexes

The reaction between an unfunctionalized conjugated diene and a nitroarene under CO pressure and at 100 °C, catalyzed by [Pd(Phen)2][BF4]2 (Phen = 1,10-phenanthroline), affords the corresponding hetero-Diels -Alder adduct (oxazine) in up to 91% yields in one pot. If the reaction mixture is then heated to 200 °C, the oxazines are converted into the corresponding N-arylpyrroles in good yields. Pressures as low as 5 bar can be employed, and 0.08% catalyst is sufficient to effect the transformation. The reaction can be equally run by employing the nitroarene or the diene as limiting agent and works well for nitroarenes bearing either electron-withdrawing or mildly electron-donating substituents. A moderate steric hindrance on the nitroarene (o-methyl) is well tolerated, but 1,4-disubstituted-1,3-dienes are not suitable substrates.